US7915332B2 - Compositions and methods for polymer composites - Google Patents
Compositions and methods for polymer composites Download PDFInfo
- Publication number
- US7915332B2 US7915332B2 US11/766,227 US76622707A US7915332B2 US 7915332 B2 US7915332 B2 US 7915332B2 US 76622707 A US76622707 A US 76622707A US 7915332 B2 US7915332 B2 US 7915332B2
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- organoclay
- polymer
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- WQTFDQBIFAATMR-UHFFFAOYSA-N O=C1C2=C(C=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2)C(=O)N1C1=CC([P+](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2)=CC=C1 Chemical compound O=C1C2=C(C=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2)C(=O)N1C1=CC([P+](C2=CC=CC=C2)(C2=CC=CC=C2)C2=CC=CC=C2)=CC=C1 WQTFDQBIFAATMR-UHFFFAOYSA-N 0.000 description 1
- NXCDKTSTTGTINW-UHFFFAOYSA-N O=C1C2=C(C=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2)C(=O)N1C1=CC=CC=C1 Chemical compound O=C1C2=C(C=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2)C(=O)N1C1=CC=CC=C1 NXCDKTSTTGTINW-UHFFFAOYSA-N 0.000 description 1
- FEASLLIXSCOBHU-UHFFFAOYSA-N O=C1C2=C(C=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2)C(=O)N1CC1CC2C3CC(CN4C(=O)C5=C(C=CC=C5)C4=O)C(C3)C2C1.O=C1C2=C(C=CC=C2)C(=O)N1CC1CC2C3CC(CN4C(=O)C5=C(C=C([P+](C6=CC=CC=C6)(C6=CC=CC=C6)C6=CC=CC=C6)C=C5)C4=O)C(C3)C2C1.[Cl-].[Cl-] Chemical compound O=C1C2=C(C=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2)C(=O)N1CC1CC2C3CC(CN4C(=O)C5=C(C=CC=C5)C4=O)C(C3)C2C1.O=C1C2=C(C=CC=C2)C(=O)N1CC1CC2C3CC(CN4C(=O)C5=C(C=C([P+](C6=CC=CC=C6)(C6=CC=CC=C6)C6=CC=CC=C6)C=C5)C4=O)C(C3)C2C1.[Cl-].[Cl-] FEASLLIXSCOBHU-UHFFFAOYSA-N 0.000 description 1
- XQEQGARSXWWIJK-UHFFFAOYSA-N O=C1C2=C(C=CC=C2)C(=O)N1C1=CC=C(S(=O)(=O)C2=CC=C(N3C(=O)C4=C(C=C([P+](C5=CC=CC=C5)(C5=CC=CC=C5)C5=CC=CC=C5)C=C4)C3=O)C=C2)C=C1 Chemical compound O=C1C2=C(C=CC=C2)C(=O)N1C1=CC=C(S(=O)(=O)C2=CC=C(N3C(=O)C4=C(C=C([P+](C5=CC=CC=C5)(C5=CC=CC=C5)C5=CC=CC=C5)C=C4)C3=O)C=C2)C=C1 XQEQGARSXWWIJK-UHFFFAOYSA-N 0.000 description 1
- GGMZYYZSGZUGMT-UHFFFAOYSA-N O=C1C2=CC=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2C(=O)N1C1=CC=C(S(=O)(=O)C2=CC=C(N3C(=O)C4=CC=C([P+](C5=CC=CC=C5)(C5=CC=CC=C5)C5=CC=CC=C5)C=C4C3=O)C=C2)C=C1 Chemical compound O=C1C2=CC=C([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)C=C2C(=O)N1C1=CC=C(S(=O)(=O)C2=CC=C(N3C(=O)C4=CC=C([P+](C5=CC=CC=C5)(C5=CC=CC=C5)C5=CC=CC=C5)C=C4C3=O)C=C2)C=C1 GGMZYYZSGZUGMT-UHFFFAOYSA-N 0.000 description 1
- FHXITYIVXRQZQM-UHFFFAOYSA-N [CH2-]OOO.[H]C(CC1=CC2=C(C=C1)C(=O)N(C1=CC([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)=CC=C1)C2=O)C1=CC=CC=C1 Chemical compound [CH2-]OOO.[H]C(CC1=CC2=C(C=C1)C(=O)N(C1=CC([P+](C3=CC=CC=C3)(C3=CC=CC=C3)C3=CC=CC=C3)=CC=C1)C2=O)C1=CC=CC=C1 FHXITYIVXRQZQM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/50—Phosphorus bound to carbon only
Definitions
- This invention relates to organic salt compositions useful in the preparation of organoclay compositions, polymer-organoclay composite compositions, and methods for the preparation of polymer nanocomposites.
- Organoclays serve as useful additives in the preparation of polymer compositions possessing enhanced physical properties relative to unfilled polymeric materials, and relative to polymer composite compositions comprising inorganic clays. Organoclays are typically prepared by replacing the inorganic cations present in the galleries between the silicate layers of a typical inorganic clay with organic cations.
- a principal advantage of the organoclay compositions is that when they are combined within a polymer composition the organoclay is found to exfoliate and interact with the polymer matrix to a greater degree than in the case of a corresponding composition comprising a purely inorganic clay.
- the presence of organic moieties between the inorganic silicate layers present in the organoclay both swells the organoclay, i.e.
- organoclay-containing polymer composition increases the d-spacing in the organoclay relative to the d-spacing in the corresponding inorganic clay, and enhances the tendency of the organoclay to exfoliate when subjected to shearing forces within a polymer matrix. In some instances exfoliation occurs so completely that a polymeric composition comprising very highly dispersed silicate layers results, and the organoclay-containing polymer composition is referred to as a nanocomposite.
- organoclay compositions are actively sought after and are highly prized when discovered.
- One deficiency in many organoclays is the thermal instability of the organic cation(s) present, making them unsuitable in applications wherein the polymer-organoclay composition must be processed at high temperature, as is the case in organoclay-containing polymer compositions comprising “high heat” polymers such as polyetherimide.
- Another deficiency of many known organoclay compositions is that the organoclay compositions may interact unfavorably with the polymer matrix when the organoclay composition is dispersed in a polymer matrix and marginal performance of the organoclay-containing polymer composition may result.
- the organic cation is a primary ammonium cation and the polymer matrix is sensitive to amine groups
- degradation of the polymer matrix may result during melt mixing, for example, of the polymer matrix with the organoclay composition.
- organoclay compositions which are both thermally stable and which interact favorably with the polymer matrix in organoclay-containing polymer compositions.
- the instant invention addresses these and other technical challenges.
- the present invention provides novel quaternary organophosphonium salts and novel quaternary pyridinium salts which are useful in the preparation of organoclay compositions.
- the present invention provides novel organoclay compositions prepared using the novel organic salts provided by the present invention.
- the present invention provides novel polymer-organoclay composite compositions comprising the organoclay compositions disclosed herein.
- the present invention provides novel methodology for the preparation of polymer-organoclay composite compositions.
- FIG. 1 shows a resulting film of this invention having a nanosilicate loading of 7%, a machine direction CTE of 33.0 ppm/° C., and a Tg of 255° C.
- solvent can refer to a single solvent or a mixture of solvents.
- Approximating language may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about”, is not to be limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value.
- aromatic radical refers to an array of atoms having a valence of at least one comprising at least one aromatic group.
- the array of atoms having a valence of at least one comprising at least one aromatic group may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen.
- aromatic radical includes but is not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl, phenylene, and biphenyl radicals.
- the aromatic radical contains at least one aromatic group.
- the aromatic radical may also include nonaromatic components.
- a benzyl group is an aromatic radical which comprises a phenyl ring (the aromatic group) and a methylene group (the nonaromatic component).
- a tetrahydronaphthyl radical is an aromatic radical comprising an aromatic group (C 6 H 3 ) fused to a nonaromatic component —(CH 2 ) 4 —.
- aromatic radical is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, haloaromatic groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylphenyl radical is a C 7 aromatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 2-nitrophenyl group is a C 6 aromatic radical comprising a nitro group, the nitro group being a functional group.
- Aromatic radicals include halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy) (i.e., —OPhC(CF 3 ) 2 PhO—), 4-chloromethylphen-1-yl, 3-trifluorovinyl-2-thienyl, 3-trichloromethylphen-1-yl (i.e., 3-CCl 3 Ph-), 4-(3-bromoprop-1-yl)phen-1-yl (i.e., 4-BrCH 2 CH 2 CH 2 Ph-), and the like.
- halogenated aromatic radicals such as 4-trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phen-1-yloxy) (i.e., —OPhC(CF 3 ) 2 PhO—), 4-chloromethylphen-1-yl, 3-trifluorovinyl-2-thienyl, 3-trich
- aromatic radicals include 4-allyloxyphen-1-oxy, 4-aminophen-1-yl (i.e., 4-H 2 NPh-), 3-aminocarbonylphen-1-yl (i.e., NH 2 COPh-), 4-benzoylphen-1-yl, dicyanomethylidenebis(4-phen-1-yloxy) (i.e., —OPhC(CN) 2 PhO—), 3-methylphen-1-yl, methylenebis(4-phen-1-yloxy) (i.e., —OPhCH 2 PhO—), 2-ethylphen-1-yl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl, hexamethylene-1,6-bis(4-phen-1-yloxy) (i.e., —OPh(CH 2 ) 6 PhO—), 4-hydroxymethylphen-1-yl (i.e., 4-HOCH 2 Ph-), 4-mer
- a C 3 -C 10 aromatic radical includes aromatic radicals containing at least three but no more than 10 carbon atoms.
- the aromatic radical 1-imidazolyl (C 3 H 2 N 2 —) represents a C 3 aromatic radical.
- the benzyl radical (C 7 H 7 —) represents a C 7 aromatic radical.
- cycloaliphatic radical refers to a radical having a valence of at least one, and comprising an array of atoms which is cyclic but which is not aromatic. As defined herein a “cycloaliphatic radical” does not contain an aromatic group.
- a “cycloaliphatic radical” may comprise one or more noncyclic components.
- a cyclohexylmethyl group (C 6 H 11 CH 2 —) is a cycloaliphatic radical which comprises a cyclohexyl ring (the array of atoms which is cyclic but which is not aromatic) and a methylene group (the noncyclic component).
- the cycloaliphatic radical may include heteroatoms such as nitrogen, sulfur, selenium, silicon and oxygen, or may be composed exclusively of carbon and hydrogen.
- the term “cycloaliphatic radical” is defined herein to encompass a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylcyclopent-1-yl radical is a C 6 cycloaliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 2-nitrocyclobut-1-yl radical is a C 4 cycloaliphatic radical comprising a nitro group, the nitro group being a functional group.
- a cycloaliphatic radical may comprise one or more halogen atoms which may be the same or different. Halogen atoms include, for example; fluorine, chlorine, bromine, and iodine.
- Cycloaliphatic radicals comprising one or more halogen atoms include 2-trifluoromethylcyclohex-1-yl, 4-bromodifluoromethylcyclooct-1-yl, 2-chlorodifluoromethylcyclohex-1-yl, hexafluoroisopropylidene-2,2-bis(cyclohex-4-yl) (i.e., —C 6 H 10 C(CF 3 ) 2 C 6 H 10 —), 2-chloromethylcyclohex-1-yl, 3-difluoromethylenecyclohex-1-yl, 4-trichloromethylcyclohex-1-yloxy, 4-bromodichloromethylcyclohex-1-ylthio, 2-bromoethylcyclopent-1-yl, 2-bromopropylcyclohex-1-yloxy (e.g., CH 3 CHBrCH 2 C 6 H 10 O—), and the like.
- cycloaliphatic radicals include 4-allyloxycyclohex-1-yl, 4-aminocyclohex-1-yl (i.e., H 2 C 6 H 10 —), 4-aminocarbonylcyclopent-1-yl (i.e., NH 2 COC 5 H 8 —), 4-acetyloxycyclohex-1-yl, 2,2-dicyanoisopropylidenebis(cyclohex-4-yloxy) (i.e., —OC 6 H 10 C(CN) 2 C 6 H 10 O—), 3-methylcyclohex-1-yl, methylenebis(cyclohex-4-yloxy) (i.e., —OC 6 H 10 CH 2 C 6 H 10 O—), 1-ethylcyclobut-1-yl, cyclopropylethenyl, 3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl, hexamethylene-1,6
- a C 3 -C 10 cycloaliphatic radical includes cycloaliphatic radicals containing at least three but no more than 10 carbon atoms.
- the cycloaliphatic radical 2-tetrahydrofuranyl (C 4 H 7 O—) represents a C 4 cycloaliphatic radical.
- the cyclohexylmethyl radical (C 6 H 11 CH 2 —) represents a C 7 cycloaliphatic radical.
- aliphatic radical refers to an organic radical having a valence of at least one consisting of a linear or branched array of atoms which is not cyclic. Aliphatic radicals are defined to comprise at least one carbon atom. The array of atoms comprising the aliphatic radical may include heteroatoms such as nitrogen, sulfur, silicon, selenium and oxygen or may be composed exclusively of carbon and hydrogen.
- aliphatic radical is defined herein to encompass, as part of the “linear or branched array of atoms which is not cyclic” a wide range of functional groups such as alkyl groups, alkenyl groups, alkynyl groups, haloalkyl groups, conjugated dienyl groups, alcohol groups, ether groups, aldehyde groups, ketone groups, carboxylic acid groups, acyl groups (for example carboxylic acid derivatives such as esters and amides), amine groups, nitro groups, and the like.
- the 4-methylpent-1-yl radical is a C 6 aliphatic radical comprising a methyl group, the methyl group being a functional group which is an alkyl group.
- the 4-nitrobut-1-yl group is a C 4 aliphatic radical comprising a nitro group, the nitro group being a functional group.
- An aliphatic radical may be a haloalkyl group which comprises one or more halogen atoms which may be the same or different.
- Halogen atoms include, for example; fluorine, chlorine, bromine, and iodine.
- Aliphatic radicals comprising one or more halogen atoms include the alkyl halides trifluoromethyl, bromodifluoromethyl, chlorodifluoromethyl, hexafluoroisopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, bromodichloromethyl, bromoethyl, 2-bromotrimethylene (e.g., —CH 2 CHBrCH 2 —), and the like.
- aliphatic radicals include allyl, aminocarbonyl (i.e., —CONH 2 ), carbonyl, 2,2-dicyanoisopropylidene (i.e., —CH 2 C(CN) 2 CH 2 —), methyl (i.e., —CH 3 ), methylene (i.e., —CH 2 —), ethyl, ethylene, formyl (i.e., —CHO), hexyl, hexamethylene, hydroxymethyl (i.e., —CH 2 OH), mercaptomethyl (i.e., —CH 2 SH), methylthio (i.e., —SCH 3 ), methylthiomethyl (i.e., —CH 2 SCH 3 ), methoxy, methoxycarbonyl (i.e., CH 3 OCO—), nitromethyl (i.e., —CH 2 NO 2 ), thiocarbonyl, trimethylsilyl (i.e.
- a C 1 -C 10 aliphatic radical contains at least one but no more than 10 carbon atoms.
- a methyl group i.e., CH 3 —
- a decyl group i.e., CH 3 (CH 2 ) 9 —
- CH 3 (CH 2 ) 9 — is an example of a C 10 aliphatic radical.
- the present invention provides an organophosphonium salt having structure I
- Ar 1 , Ar 2 , and Ar 3 are independently C 2 -C 50 aromatic radicals;
- Ar 4 is a bond or a C 2 -C 50 aromatic radical;
- “a” is a number from 1 to about 200;
- “c” is a number from 0 to 3;
- R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
- R 2 is a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 2 -C 50 aromatic radical, or a polymer chain;
- X ⁇ is a charge balancing counterion.
- each of Ar 1 -Ar 3 is a phenyl radical (C 6 H 5 —)
- Ar 4 is a meta-phenylene radical
- the variable “c” is zero
- the variable “a” is 2
- X ⁇ is iodide
- the group R 2 is the divalent C 15 aromatic radical —OC- 6 H 4 C 3 H 6 C 6 H 4 O—.
- the group represented by R 2 in structure I is a polyetherimide polymer chain (See for example Entry 1i of Table I).
- the group represented by R 2 in structure I is a polyether ketone polymer chain.
- the group represented by R 2 in structure I is a polyether sulfone polymer chain
- the polymer chain may be of high molecular weight or low molecular weight.
- High molecular weight polymer chains are those having a number average molecular weight (M n ) of greater than 8,000 grams per mole as measured by gel permeation chromatography using polystyrene molecular weight standards.
- Low molecular weight polymer chains are those having a number average molecular weight (M n ) of 8,000 grams per mole or less as measured by gel permeation chromatography using polystyrene molecular weight standards.
- the present invention provides a organophosphonium salt having structure I wherein R 2 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 50,000 grams per mole as determined by gel permeation chromatography. In another embodiment, R 2 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 20,000 grams per mole as determined by gel permeation chromatography. In yet another embodiment, R 2 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 5,000 grams per mole as determined by gel permeation chromatography.
- the present invention provides an organophosphonium salt having structure II
- X ⁇ is a charge balancing counterion
- the present invention provides an organophosphonium salt having structure III
- X ⁇ is a charge balancing counterion
- the present invention provides an organophosphonium salt having structure IV
- X ⁇ is a charge balancing counterion
- m is a number in a range from about 10 to about 1000
- Ar 5 is a C 2 -C 50 aromatic radical, or a polymer chain.
- the present invention provides an organophosphonium salt having structure IV wherein the group Ar 5 has structure V
- X ⁇ is a charge balancing counterion
- X ⁇ represents a charge balancing counterion.
- X ⁇ represents a charge balancing counterion which is a monovalent, divalent, or trivalent anionic species.
- X ⁇ is selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, sulfite, carbonate, bicarbonate, acetate, oxalate, and combinations thereof.
- the inorganic anions fluoride, chloride, bromide, iodide, and bicarbonate are examples of monovalent anions.
- the inorganic anions carbonate and sulfate and the organic anion oxalate are examples of divalent anions.
- the trianion of Kemp's triacid is an example of a trivalent anion.
- the novel organophosphonium salts provided by the present invention may be prepared by a variety of methods.
- the experimental section of this disclosure provides a number of specific methods and conditions for the preparation of organophosphonium salts having structure I.
- the organophosphonium salt may be prepared by reacting an aryl halide with a triarylphosphine, optionally in the presence of a catalyst, such as palladium(II) acetate.
- a catalyst such as palladium(II) acetate.
- an amine-substituted phosphonium salt is reacted with an anhydride to provide an imide-containing product comprising a phosphonium salt moiety.
- the present invention provides a method for the preparation of an organophosphonium salt comprising (a) contacting an amine-substituted phosphonium salt having structure VI
- Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently C 2 -C 50 aromatic radicals, and X ⁇ is a charge balancing counterion; with an anhydride compound having structure VII
- “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 2 is a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 2 -C 50 aromatic radical, or a polymer chain; and (b) isolating the product organophosphonium salt.
- compound VI is an aniline bearing a triphenylphosphonium moiety meta to the amine (NH 2 ) group, and wherein the charge balancing counterion is iodide.
- compound VI is an aniline bearing a triphenylphosphonium moiety para to the amine (NH 2 ) group, and wherein the charge balancing counterion is chloride.
- the anhydride compound VII is selected from the group consisting of bisphenol A dianhydride (BPADA), 4,4′-biphenyl dianhydride, and 4,4′-oxydiphthalic anhydride (4,4′-ODPA).
- BPADA bisphenol A dianhydride
- 4,4′-ODPA 4,4′-oxydiphthalic anhydride
- anhydride compound VII is bisphenol A dianhydride.
- the anhydride compound VII is a polymeric dianhydride comprising anhydride terminal groups, said polymeric dianhydride being a polyetherimide derived from BPADA and meta-phenylene diamine, said polymeric dianhydride having a number average molecular weight M n of about 10,000 grams per mole.
- the reaction (“contacting”) between the amine-substituted phosphonium salt having structure VI and the anhydride compound having structure VII takes place in a solvent at a temperature in excess of 100° C. with the removal of water formed as a by-product in the condensation reaction.
- the reaction is carried out in an organic solvent at temperature in a range from about 120° C. to about 160° C.
- the reaction is carried out in a melt.
- a catalyst such as are used in imidization reactions, for example sodium phenyl phosphinate (SPP).
- SPP sodium phenyl phosphinate
- Suitable solvents include oDCB (orthodichorobenzene), toluene, xylene, chlorobenzene, anisole, veratrole, and combinations thereof.
- the present invention provides a method for the preparation of an organophosphonium salt comprising (a) contacting an amine-substituted phosphonium salt having structure IX
- a is a number from 1 to about 200; “c” is a number from 0 to 3; R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and R 2 is a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 2 -C 50 aromatic radical, or a polymer chain; and (b) isolating the product organophosphonium salt.
- the anhydride compound having structure VII is selected from the group consisting of 4,4′-oxydiphthalic anhydride, 3,4′-oxydiphthalic anhydride, 3,3′-oxydiphthalic anhydride, bisphenol A dianhydride, 6F-dianhydride, 3,4′-biphenyl dianhydride, 4,4′-biphenyl dianhydride, and combinations thereof.
- the present invention provides a method of preparing an organophosphonium salt comprising (a) contacting an aromatic amine with a halogen-substituted anhydride to provide a halogen-substituted imide; (b) reacting said halogen-substituted imide with a triarylphosphine to effect a nucleophilic substitution of halogen by triarylphosphine; and (c) isolating the product organophosphonium salt.
- the halogen-substituted anhydride is selected from the group consisting of 3-chlorophthalic anhydride (3-ClPA), 4-chlorophthalic anhydride (4-ClPA), 3-fluorophthalic anhydride, and 4-fluorophthalic anhydride.
- the halogen-substituted anhydride comprises 4-chlorophthalic anhydride.
- the halogen-substituted anhydride comprises a mixture of 3-chlorophthalic anhydride and 4-chlorophthalic anhydride.
- the aromatic amine may be a monoamine or a polyamine.
- the aromatic amine is a polymer comprising amine groups.
- Monoamines are illustrated by aniline, 1-aminonaphthalene, 3-chloroaniline, 4-chloroaniline, 2,4-dichloroaniline, 4-chloro-4′-aminobiphenyl, and the like.
- Suitable triarylphosphines include triphenylphosphine, tolylphosphine, trixylylphosphine, tris(4-t-butoxyphenyl)phosphine, and the like.
- the present invention provides novel pyridinium salt having structure XV
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group; and X ⁇ is a charge balancing counterion.
- pyridinium salts encompassed by structure XV are useful in the preparation of organoclay compositions and polymer-organoclay composite compositions.
- Representative pyridinium salts encompassed by generic structure XV are illustrated in Table II.
- the pyridinium salt of Entry 2a of Table II represents a pyridinium salt having structure XV wherein Ar 6 , Ar 7 , and Ar 8 are each phenyl; “b” is 0; “d” is 2; R 4 is methyl; Z is an oxygen linking group; Ar 9 is a C 12 aromatic radical; and X ⁇ is a chloride ion.
- the pyridinium salt of Entry 2b of Table II represents a pyridinium salt having structure XV wherein Ar 6 , Ar 7 , and Ar 8 are phenyl; “b” is 0; “d” is 0; Z is an oxygen linking group; Ar 9 is a C 12 aromatic radical; and X ⁇ is an acetate ion.
- the present invention provides a pyridinium salt having structure XV wherein Ar 9 is a polyetherimide polymer chain. In another embodiment, the present invention provides a pyridinium salt having structure XV wherein Ar 9 is a polyether ketone polymer chain. In one embodiment, Ar 9 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 50,000 grams per mole. In another embodiment, Ar 9 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 20,000 grams per mole.
- Ar 9 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 5,000 grams per mole. In another embodiment, Ar 9 is a polyetherimide polymer chain having a number average molecular weight M n in a range from about 1000 to about 20,000 grams per mole.
- Ar 9 is a polyetherimide polymer chain having a number average molecular weight M n in a range from about 1000 to about 50,000 grams per mole.
- the present invention provides a pyridinium salt encompassed by generic structure XV having structure XVI
- X ⁇ is independently at each occurrence a charge balancing counterion.
- X ⁇ is BF 4 ⁇ .
- the present invention provides a pyridinium salt having structure XVII
- X ⁇ is independently at each occurrence a charge balancing counterion.
- X ⁇ is acetate.
- the present invention provides a pyridinium salt having structure XVIII
- X ⁇ is a charge balancing counterion; “e” is a number in a range from about 10 to about 1000; and Ar 10 is a C 2 -C 50 aromatic radical, or a polymer chain.
- X ⁇ is the tetrafluoroborate (BF 4 ⁇ ) anion, the variable “e” is about 100, and Ar 10 is the C 25 -aromatic radical 2,4,6-triphenylpyridinium tetrafluoroborate.
- an aromatic radical may include an associated counterion, here BF 4 ⁇ , and still fall within the definition of the term aromatic radical as defined herein.
- aliphatic radicals and cycloaliphatic radicals may include an associated counterion as well.
- a radical comprises multiple charges requiring the presence of a charge balancing counterion
- a plurality of charge balancing counterions may be comprised within the radical.
- a fractional part of a charge balancing counterion may be comprised within a radical as well.
- a single sulfate anion may be associated with two individual molecules or radicals.
- Ar 10 is an aromatic radical having structure XIX
- X ⁇ is a charge balancing counterion.
- X ⁇ is a fractional part of a divalent ion selected from the group consisting of sulfate, carbonate, and oxalate.
- Charge balancing counterions which may be present in pyridinium salt structure XV include those disclosed herein for structure I.
- the charge balancing counterion is selected from the group consisting of fluoride, chloride, bromide, iodide, sulfate, sulfite, carbonate, bicarbonate, acetate, oxalate, and combinations thereof.
- the present invention provides a method for the preparation of a pyridinium salt having structure XV comprising (a) contacting an aromatic amine having structure XX
- R 4 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical
- Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group
- Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group
- X ⁇ is a charge balancing counterion; with a pyrilium salt having structure XXI
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and X ⁇ is a charge balancing counterion; and (b) isolating the product pyridinium salt having structure XV.
- the reaction brought about by contacting aromatic amine XX with pyrilium salt XXI typically involves contacting these reactants at a temperature in a range from about ⁇ 20° C. to about 150° C. Although a solvent is typically employed, the reaction may be carried out in a melt as well.
- the present invention provides a polymeric pyridinium salt and a method for its preparation.
- the polymeric pyridinium salt may be prepared by (a) reacting (contacting) a polymeric aromatic diamine with a pyrilium salt having structure XXI, and (b) isolating the product polymeric pyridinium salt.
- the said polymeric aromatic diamine comprises structural units derived from at least one non-polymeric aromatic diamine and at least one dianhydride.
- a molar excess of a diamine such as 4,4′-oxydianiline (4,4′-ODA) may be reacted with 4,4′-oxydiphthalic anhydride (4,4′-ODPA) in orthodichorobenzene (oDCB) at reflux to provide an amine terminated polyetherimide.
- oDCB orthodichorobenzene
- Reaction of the amine terminated polyetherimide with a pyrilium salt having structure XXI affords the product polymeric pyridinium salt which may be isolated by, for example, antisolvent precipitation.
- the non-polymeric aromatic diamine is meta-phenylenediamine. In one embodiment, the non-polymeric aromatic diamine is meta-phenylenediamine and the dianhydride is BPADA. In one embodiment, the dianhydride employed is a mixture of BPADA and 4,4′-ODPA.
- the present invention provides a polymeric pyridinium salt having structure XXII
- f is a number from 10 to about 1000
- X ⁇ is a charge balancing counterion
- the present invention provides a method comprising (a) contacting a polymeric aromatic diamine having structure XXIII
- variable “f” is a number from 10 to about 1000; with a pyrilium salt having structure XXIV
- polymeric diamines such as XXIII may be prepared by reacting an excess of an aromatic diamine with a dianhydride under condensation polymerization conditions (for example refluxing oDCB).
- a dianhydride under condensation polymerization conditions
- diamine XXIII may be prepared by reacting excess meta-phenylene diamine with 4,4′-ODPA under condensation polymerization conditions.
- Pyrilium salts such as XXIV are available commercially or may be prepared by methods known in the art.
- the present invention provides a polymeric pyridinium salt having structure XXII wherein the variable “f” is a number from 10 to about 100.
- the present invention provides access to other organic salts useful in the preparation of organoclay compositions and polymer-organoclay composite composition derived from said organoclay compositions.
- the present invention provides access to pyridinium salts comprising cation XXV
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Pyridinium salts comprising cation XXV are illustrated in Table III. Pyridinium salts comprising cation XXV may be prepared and incorporated into organoclay compositions and polymer-organoclay composite compositions using methods disclosed herein. For example those methods suitable for the preparation and use of pyridinium salts having structure XV, may be applied to the preparation and use of pyridinium salts comprising cation XXV.
- the present invention provides access to phenone-containing organic salts useful in the preparation of organoclay compositions and polymer-organoclay composite compositions derived from said organoclay compositions.
- the present invention provides access to phenone-containing salts comprising quaternary phosphonium cations having structure XXXIII
- Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 2 -C 50 aromatic radicals; and Ar 16 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Phenone-containing salts comprising a quaternary phosphonium cation having structure XXXIII are illustrated in Table IV. Phenone-containing salts comprising quaternary phosphonium cation XXXIII may be prepared as disclosed herein. Phenone-containing salts comprising quaternary phosphonium cation XXXIII may be incorporated into organoclay compositions and polymer-organoclay composite compositions using methods disclosed herein and shown to be suitable for organophosphonium salts I and pyridinium salts XV.
- organophosphonium salts I may be incorporated into organoclay compositions.
- phenone-containing salts comprising quaternary phosphonium cation XXXIII in the preparation of organoclay compositions.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polyether ketone polymer chain.
- a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polyether ketone polymer chain.
- Such salt compositions may be prepared, for example by reacting a polyetherketone comprising one or more terminal chlorobenzoyl groups with a triarylphosphine, for example triphenylphosphine, in a solvent and optionally in the presence of a catalyst.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 50,000 grams per mole.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 20,000 grams per mole.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polymer chain having a number average molecular weight M n in a range from about 1000 to about 5,000 grams per mole.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polyetherimide polymer chain having a number average molecular weight M n in a range from about 1000 to about 50,000 grams per mole.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIII wherein Ar 16 is a polyetherimide polymer chain having a number average molecular weight M n in a range from about 1000 to about 20,000 grams per mole.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXIV.
- a phenone-containing salt comprising quaternary phosphonium cation XXXIV.
- cation falls within the scope of the genus defined by structure XXXIII.
- structure XXXIV represents the case wherein Ar 15 of structure XXXIII is orthophenyleneoxy and Ar 16 is 4-(2-triphenylphosphonium phenyleneoxy)phenyl.
- the present invention provides access to a phenone-containing salt comprising quaternary phosphonium cation XXXV.
- the present invention provides a polymeric phenone-containing salt comprising a polymeric quaternary phosphonium cation having structure XXXVII
- W is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group;
- R 5 and R 6 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
- i is a number from about 10 to about 1000; and
- Ar 17 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Polymeric phenone-containing salts comprising a polymeric quaternary phosphonium cation having structure XXXVII are illustrated in Table V below.
- Ar 17 is an aromatic radical comprising structure XXXVIII.
- Polymeric phenone-containing salts such as those illustrated in Table V may be prepared by from the corresponding halogen-substituted polyetherketones by reaction with a triarylphosphine as described herein.
- Halogen-substituted polyetherketones are available by methods known to one of ordinary skill in the art and can be prepared, for example, by reacting the disodium salt of a bisphenol (e.g. the disodium salt of bisphenol A) with a molar excess (e.g. 5 mole percent excess) of a dihalo benzophenone (e.g. 4,4′-difluorobenzophenone) in an inert solvent (e.g. orthodichorobenzene) at elevated temperature (e.g. 130-180° C.) in the presence of phase transfer catalyst (e.g. hexaethyl guanidinium chloride).
- phase transfer catalyst e.g. hexaethyl guanidinium chloride
- the present invention provides an organoclay composition comprising a quaternary organic cation.
- the quaternary organic cation may be a quaternary phosphonium cation, a quaternary ammonium cation, or a combination thereof.
- Quaternary organic cations are the cationic components of the various quaternary organic salts disclosed herein.
- organophosphonium salt I is a quaternary organic salt comprising the quaternary organic cation X
- Ar 1 , Ar 2 , and Ar 3 are independently C 2 -C 50 aromatic radicals;
- Ar 4 is a bond or a C 2 -C 50 aromatic radical;
- “a” is a number from 1 to about 200;
- “c” is a number from 0 to 3;
- R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and
- R 2 is a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 2 -C 50 aromatic radical, or a polymer chain.
- pyridinium salt XV is a quaternary organic salt comprising the quaternary organic cation XXVI
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; and Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; Ar 11 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group; and X ⁇ is a charge balancing counterion; is a quaternary organic salt comprising quaternary organic cation XXV
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 2 -C 50 aromatic radicals;
- Ar 16 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group; and
- X ⁇ is a charge balancing counterion; is a quaternary organic salt comprising a quaternary organic cation having structure
- Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 2 -C 50 aromatic radicals; and Ar 16 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- the aromatic radical Ar 1 as defined in organophosphonium salt I has the same meaning as aromatic radical Ar 1 in organophosphonium cation X.
- Ar 1 is a phenyl group in organophosphonium salt I, it is also a phenyl group in organophosphonium cation X.
- the organoclay compositions of the present invention comprise alternating inorganic silicate layers and organic layers.
- the inorganic silicate layers may be derived from any suitable source, for example natural clay.
- the inorganic silicate layers are derived from synthetic clay. Suitable clays include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, and combinations thereof.
- the inorganic silicate layers are derived from montmorillonite clay.
- the organoclay compositions provided by the present invention are characterized by an interlayer distance between the inorganic silicate layers of from 5 to about 100 Angstroms. In one embodiment, the organoclay compositions provided by the present invention are characterized by an interlayer distance between the inorganic silicate layers of from 10 to about 100 angstroms, and in another embodiment from about 20 to about 100 angstroms.
- the organoclay composition provided by the present invention are prepared by (a) contacting in a first reaction mixture a quaternary organic salt with a layered silicate in the presence of a solvent, and (b) isolating the product organoclay composition.
- the quaternary organic salt is a organophosphonium salt having structure I.
- the quaternary organic salt is a pyridinium salt having structure XV.
- the quaternary organic salt is a pyridinium salt having structure XXXI.
- the quaternary organic salt is a phenone-containing organophosphonium salt having structure XXXVI.
- the organoclay compositions provided by the present invention may be prepared by contacting a quaternary organic salt with a layered silicate in the presence of a solvent.
- the layered silicate is a natural clay.
- the layered silicate is a synthetic clay.
- the layered silicate comprises an inorganic clay selected from the group consisting of kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, and combinations thereof.
- the layered silicate comprises montmorillonite clay.
- the organoclay compositions provided by the present invention may be prepared by contacting a quaternary organic salt with a layered silicate in the presence of a solvent.
- the solvent employed comprises an organic solvent, for example acetone.
- the solvent employed comprises water.
- the solvent employed comprises both water and an organic solvent, for example aqueous methanol containing about 10 percent by weight water and about 90 percent by weight methanol.
- the organoclay composition may be isolated using conventional techniques such as filtration, centrifugation, antisolvent precipitation, decantation, and the like. Various techniques suitable for isolating the organoclay compositions provided by the present invention are disclosed in the experimental part of this disclosure.
- the present invention provides an organoclay composition
- organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure X
- Ar 1 , Ar 2 , and Ar 3 are independently C 2 -C 50 aromatic radicals;
- Ar 4 is a bond or a C 2 -C 50 aromatic radical;
- “a” is a number from 1 to about 200;
- “c” is a number from 0 to 3;
- R 1 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and
- R 2 is a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, a C 2 -C 50 aromatic radical, or a polymer chain.
- Organophosphonium cations X are illustrated by the cationic components of the organophosphonium salts disclosed in Table I.
- the quaternary phosphonium cation has structure XI.
- the quaternary phosphonium cation has structure XII.
- the present invention provides an organoclay composition comprising a polymeric quaternary phosphonium cation. In one embodiment, the present invention provides an organoclay composition comprising a polymeric quaternary phosphonium cation having structure XIII
- m is a number in a range from about 10 to about 1000; and Ar 5 is a C 2 -C 50 aromatic radical, or a polymer chain.
- Ar 5 is an aromatic radical having structure XIV.
- the present invention provides an organoclay composition
- an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXV
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; R 3 is independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and Ar 11 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Pyridinium cations having structure XXV are illustrated by the cationic components of the pyridinium salts disclosed in Table III herein.
- the present invention provides an organoclay composition
- organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXVI
- Ar 6 , Ar 7 , and Ar 8 are independently C 2 -C 50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R 3 and R 4 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; Z is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group; and Ar 9 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Pyridinium cations having structure XXVI are illustrated by the cationic components of the pyridinium salts disclosed in Table II herein.
- the present invention provides an organoclay composition comprising a pyridinium cation having structure XXVII.
- the present invention provides an organoclay composition comprising a pyridinium cation having structure XXVIII.
- the organoclay composition provided by the present invention comprises a polymeric quaternary organic cation which is a polymeric pyridinium cation.
- the polymeric pyridinium cation comprises structure XXIX
- variable “e” is a number from about 10 to about 1000; and Ar 10 is a C 2 -C 50 aromatic radical, or a polymer chain. In one embodiment, Ar 10 is a C 23 aromatic radical having structure XXX.
- the present invention provides an organoclay composition
- an organoclay composition comprising a polymeric pyridinium cation having structure XXXII
- f is a number from about 10 to about 1000. In a particular embodiment, “f” has a value of about 10. In another particular embodiment, “f” has a value of about 30.
- the present invention provides an organoclay composition
- organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XXXIII
- Ar 12 , Ar 13 , Ar 14 and Ar 15 are independently C 2 -C 50 aromatic radicals; and Ar 16 is a C 2 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Quaternary phosphonium cation having structure XXXIII are at times herein referred to as “phenone-containing organophosphonium cations”. Quaternary phosphonium cations having structure XXXIII are illustrated by the cationic components of the organophosphonium salts disclosed in Table IV herein.
- the present invention provides an organoclay composition comprising a quaternary phosphonium cation having structure XXXIV.
- the present invention provides an organoclay composition comprising a quaternary phosphonium cation having structure XXXV.
- the present invention provides an organoclay composition
- W is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group;
- R 5 and R 6 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical;
- “i” is a number from about 10 to about 1000; and
- Ar 17 is a C 10 -C 200 aromatic radical, or a polymer chain comprising at least one aromatic group.
- Ar 17 is an aromatic radical having structure XXXVIII.
- Polymeric quaternary phosphonium cations having structure XXXVII are illustrated by the cationic components of the polymeric organophosphonium salts disclosed in Table V herein.
- the present invention provides a polymer-organoclay composite composition
- a polymer-organoclay composite composition comprising (a) a polymeric resin and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, wherein the organic layers comprise a quaternary organic cation.
- the polymeric resin comprises an amorphous thermoplastic polymer. In another embodiment, the polymeric resin comprises a crystalline thermoplastic polymer. In another embodiment, the polymeric resin comprises an amorphous thermoplastic polymer and a crystalline thermoplastic polymer.
- Amorphous thermoplastic polymers are illustrated by PPSU (polyphenylene sulfone), PEI (polyetherimide), PES (polyethersulfone), PC (Polycarbonate), PPO (polyphenylene ether), PMMA (poly methyl methacrylate), ABS, (acrylonitrile butadiene styrene), and PS (polystyrene).
- Crystalline thermoplastic resins are illustrated by PFA (perfluoro alkoxyalkane), MFA (co-polymer of tetrafluoro ethylene and perfluorinated vinyl ether), FEP (fluorinated ethylene propylene polymers), PPS (polyphenylene sulfide), PEK (polyether ketone), PEEK (polyether-ether ketone), ECTFE (ethylene chloro trifluoro ethylene), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PET (polyethylene terephthalate), POM (polyacetal), PA (polyamide), UHMW-PE (ultra high molecular weight polyethylene), PP (polypropylene), PE (polyethylene), HDPE (high density polyethylene), LDPE (low density polyethylene) and advanced engineering resins such as PBI (polybenzimidizole) and PAI (polyamide-imide), polyphenylenes, poly
- the polymeric resin is selected from the group consisting of polyetherimides, polyamides, polyesters, polyarylene sulfides, polyarylene ethers, polyether sulfones, polyether ketones, polyether ether ketones, polyphenylenes, polycarbonates, and a combination comprising at least one of the foregoing polymers.
- the polymeric resin comprises a polyetherimide resin, for example ULTEM, available from GE Plastics, Inc.
- the polymeric resin comprises a polyphenylene resin, for example PRIMOSPIRE, available through Solvay, Inc.
- the polymeric resin comprises polyether sulfone, for example RADEL A, available from Solvay, Inc.
- the polymeric resin comprises a polyether ketone.
- the organoclay composition present in the polymer-organoclay composite composition is preferably highly exfoliated, meaning that the distance between inorganic silicate layers is large relative to the distance between the corresponding silicate layers in the same organoclay composition prior to its incorporation into the polymer matrix of the polymer-organoclay composite composition.
- the organoclay compositions provided by the present invention are designed to promote relatively facile separation of the silicate layers as the organoclay composition is subjected to a shearing force in the presence of a polymeric resin or a solvent.
- the polymer-organoclay composite composition provided by the present invention comprises an organoclay composition comprising alternating inorganic silicate layers and organic layers wherein the alternating inorganic silicate layers are highly dispersed relative to the organoclay composition from which the silicate layers of the polymer-organoclay composite composition are derived.
- the polymer-organoclay composite composition provided by the present invention comprises inorganic silicate layers derived from an inorganic clay selected from the group consisting of kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, and combinations thereof.
- an inorganic clay selected from the group consisting of kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, he
- the inorganic clay is first converted to an organoclay composition and the intermediate organoclay composition is then used in the preparation of the polymer-organoclay composite composition.
- the organoclay composition employed in the preparation of the polymer-organoclay composite composition is characterized by an interlayer distance of from about 5 to about 100 Angstroms. Although a substantial amount of the organoclay composition employed may be highly exfoliated in the polymer-organoclay composite composition, at least a portion of the organoclay composition employed retains an interlayer distance in the 5 to about 100 Angstrom range.
- the present invention provides an article comprising a polymer-organoclay composite composition provided by the present invention.
- the article is a film.
- the article is an extruded film.
- the article is a solvent cast film. Extruded films can be prepared using techniques described herein. Solvent cast films comprising a polymer-organoclay composite composition of the present invention may be prepared by art recognized methods.
- the present invention provides a solvent cast film comprising a polyetherimide having a dianhydride component and a diamine component and a glass transition temperature (Tg) between about 180° C. and 450° C., and wherein the film has: a) a CTE of less than 70 ppm/° C.; b) a thickness of between about 0.1 ⁇ m and 250 ⁇ m; and, c) contains less than 5% residual solvent by weight.
- Tg glass transition temperature
- the present invention provides a polymer-organoclay composite composition
- a polymeric resin which is a polyetherimide having a dianhydride component and a diamine component.
- the polyetherimide comprises structural units derived from at least one dianhydride and at least one diamine.
- Polyetherimides having a dianhydride component and a diamine component and a required Tg can be prepared by reacting one or more diamines with one or more dianhydrides under condensation polymerization conditions (e.g. refluxing orthodichorobenzene in a reaction vessel equipped to remove water of reaction in the presence of a catalyst sodium phenyl phosphinate (SPP)).
- condensation polymerization conditions e.g. refluxing orthodichorobenzene in a reaction vessel equipped to remove water of reaction in the presence of a catalyst sodium phenyl phosphinate (SPP)
- Suitable dianhydrides include:
- Suitable diamines include: ethylenediamine; propylenediamine; trimethylenediamine; diethylenetriamine; triethylenetetramine; hexamethylenediamine; heptamethylenediamine; octamethylenediamine; nonamethylenediamine; decamethylenediamine; 1,12-dodecanediamine; 1,18-octadecanediamine; 3-methylheptamethylenediamine; 4,4-dimethylheptamethylenediamine; 4-methylnonamethylenediamine; 5-methylnonamethylenediamine; 2,5-dimethylhexamethylenediamine; 2,5-dimethylheptamethylenediamine; 2,2-dimethylpropylenediamine; N-methyl-bis(3-aminopropyl)amine; 3-methoxyhexamethylenediamine; 1,2-bis(3-aminopropoxy)ethane; bis(3-aminopropyl)sulfide; 1,4-cyclohex
- the polymer-organoclay composite compositions provided by the present invention comprise an organoclay composition.
- the organoclay compositions employed are those organoclay compositions provided by the present invention.
- the polymer-organoclay composite composition comprises at least one organoclay composition comprising a quaternary organic cation selected from the group consisting of organophosphonium cations having structure X, pyridinium cations having structure XXV, pyridinium cations having structure XXVI, and phenone-containing organophosphonium cations having structure XXXIII.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure X.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XI.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XII.
- the present invention provides an article comprising a polymer-organoclay composite composition, said composition comprising (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure X.
- the present invention provides a method for the preparation of a polymer-organoclay composite composition, said method comprising contacting under melt mixing conditions a polymeric resin and an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure X.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXV.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXVI.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXVII.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXVIII.
- the present invention provides an article comprising a polymer-organoclay composite composition, said composition comprising (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXV.
- the present invention provides an article comprising a polymer-organoclay composite composition, said composition comprising (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXVI.
- the present invention provides a method for the preparation of a polymer-organoclay composite composition, said method comprising contacting under melt mixing conditions a polymeric resin and an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXV.
- the present invention provides a method for the preparation of a polymer-organoclay composite composition, said method comprising contacting under melt mixing conditions a polymeric resin and an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a pyridinium cation having structure XXVI.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XXXIII.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XXXIV.
- the present invention provides a polymer-organoclay composite composition (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XXXV.
- the present invention provides an article comprising a polymer-organoclay composite composition, said composition comprising (a) a polymeric resin; and (b) an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XXXIII.
- the present invention provides a method for the preparation of a polymer-organoclay composite composition, said method comprising contacting under melt mixing conditions a polymeric resin and an organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary phosphonium cation having structure XXXIII.
- the present invention provides a method for the preparation of a polymer-organoclay composite composition
- a method for the preparation of a polymer-organoclay composite composition comprising melt mixing a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation with a polymeric resin at a temperature in a range between about 300° C. and about 450° C. to provide a polymer-organoclay composite composition, said polymer-organoclay composite composition being characterized by a percent exfoliation of at least 10 percent.
- a quaternary organoclay composition is an organoclay composition comprising a quaternary organic cation, for example, an organophosphonium cation having structure X.
- the quaternary organic cation employed, other than it must be sufficiently stable during the melt mixing step to enable a significant level of exfoliation of the organoclay composition in the polymer matrix.
- a quaternary organic cation is considered stable if more than about 90 percent of the quaternary organic cation remains following a melt mixing step of duration and intensity sufficient to achieve a percent exfoliation of at least 10 percent.
- the quaternary organic cation has structure XXXIX
- the quaternary organic cation having structure XXXIX is a quaternary phosphonium cation, for example the tetraphenyl phosphonium cation, TPP.
- the quaternary organic cation having structure XXXIX is a quaternary phosphonium cation having structure X.
- the quaternary organic cation having structure XXXIX is a quaternary phosphonium cation having structure XXIII.
- the quaternary organic cation having structure XXXIX is a quaternary ammonium cation, for example the tetraphenylammonium cation, TPA.
- the quaternary organic cation is a pyridinium cation having structure XXV. In another embodiment, the quaternary organic cation is a pyridinium cation having structure XXVI.
- the inorganic silicate layers are derived from an inorganic clay selected from the group consisting of kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite chlorite, and combinations thereof.
- the inorganic clay is first converted to an organoclay composition comprising the quaternary organic cation.
- the organoclay composition may be prepared in the presence of the polymeric resin. Suitable organoclay compositions include those organoclay compositions disclosed herein. In one embodiment, the organoclay composition employed is characterized by an interlayer distance of from about 5 to about 100 Angstroms. Under such circumstances, at least a portion of the product polymer-organoclay composite composition will be characterized by a an interlayer distance of from about 5 to about 100 Angstroms as well.
- the polymer-organoclay composite composition prepared by melt mixing a quaternary organoclay composition comprising a quaternary organic cation with a polymeric resin at a temperature in a range between about 300° C. and about 450° C. comprises a polyarylene sulfide, for example polyphenylene sulfide (PPS).
- PPS polyphenylene sulfide
- the polymer-organoclay composite composition prepared by melt mixing a quaternary organoclay composition comprising a quaternary organic cation with a polymeric resin at a temperature in a range between about 300° C. and about 450° C. comprises a polyether ketone, for example a copolymer comprising structural units derived from bisphenol A and 4,4′-dichlorobenzophenone.
- the melt mixing may be carried out using any melt mixing technique which combines the ability to heat the organoclay composition and the polymeric resin at a temperature in a range between about 300° C. and about 450° C. under sufficient shear to achieve a percent exfoliation of the organoclay composition in the polymeric resin of at least 10 percent.
- an extruder may be used to effect melt mixing.
- the extruder is a vented, twin-screw extruder.
- the extruder is a vented, single screw reciprocating extruder.
- melt mixing is carried out in a kneader.
- melt mixing is of sufficient duration and intensity to achieve a percent exfoliation of the organoclay composition in the polymeric resin of at least 20 percent. In yet another embodiment, melt mixing is of sufficient duration and intensity to achieve a percent exfoliation of the organoclay composition in the polymeric resin of at least 30 percent.
- the present invention provides an article comprising a polymer-organoclay composite composition prepared by melt mixing (a) a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, the organic layers comprising a quaternary organic cation; with (b) a polymeric resin a temperature in a range between about 300° C. and about 450° C. under sufficient shear to achieve a percent exfoliation of the organoclay composition in the polymeric resin of at least 10 percent.
- the present invention provides a method of making a polymer-organoclay composite composition
- a method of making a polymer-organoclay composite composition comprising melt mixing a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation with a polymeric resin comprising at least one polymer selected from the group consisting of polyamides, polyesters, polyarylene sulfides, polyarylene ethers, polyether sulfones, polyether ketones, polyether ether ketones, polyphenylenes, and polycarbonates, said polymeric resin being substantially free of polyetherimides; said melt mixing being carried out at a temperature in a range between about 300° C. and about 450° C.
- a polymeric resin is substantially free of polyetherimides when it contains less than 5 weight percent polyetherimide based upon a total weight of the polymeric resin. Polymeric resins which contain 0 weight percent polyetherimide are also said to be substantially free of polyetherimides.
- the present invention provides an article comprising a polymer-organoclay composite composition, the polymer-organoclay composite composition comprising (a) a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, the organic layers comprising a quaternary organic cation; and (b) a polymeric resin comprising at least one polymer selected from the group consisting of polyamides, polyesters, polyarylene sulfides, polyarylene ethers, polyether sulfones, polyether ketones, polyether ether ketones, polyphenylenes, and polycarbonates; the polymeric resin being substantially free of polyetherimides; wherein the polymer-organoclay composite composition is characterized by a percent exfoliation of at least 10 percent.
- the article is a film.
- the article is a solvent cast film comprising a polyetherimide having a dianhydride component and a diamine component and a Tg of between about 180° C. and 450° C., and wherein the film has: a) a CTE of less than 70 ppm/° C.; b) a thickness of between about 0.1 ⁇ m and 250 ⁇ m; and, c) contains less than 5% residual solvent by weight.
- the present invention provides a method for making a polymer-organoclay composite composition
- a method for making a polymer-organoclay composite composition comprising melt mixing in an extruder, a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation with a polymeric resin comprising a polyether sulfone, said polymeric resin being substantially free of polyetherimide; said melt mixing being carried out at a temperature in a range between about 300° C. and about 450° C. to provide a polymer-organoclay composite composition, said polymer-organoclay composite composition being characterized by a percent exfoliation of at least 10 percent.
- the quaternary organic cation has structure X.
- the quaternary organic cation has structure XXV.
- the quaternary organic cation has structure XXVI.
- the quaternary organic cation has structure XX
- the present invention provides a method of making a polymer-organoclay composite composition
- a method of making a polymer-organoclay composite composition comprising melt mixing a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation with a polyetherimide composition; said melt mixing being carried out at a temperature in a range between about 300° C. and about 450° C. to provide a polymer-organoclay composite composition, said polymer-organoclay composite composition being characterized by a percent exfoliation of at least 10 percent.
- the quaternary organic cation has structure X.
- the quaternary organic cation has structure XXV.
- the quaternary organic cation has structure XXVI. In yet another embodiment, the quaternary organic cation has structure XXXIII.
- the polyetherimide composition further comprises at least one polymer selected from the group consisting of polyvinyl chloride, a polyolefin, a polyester, a polyamide, a polysulfone, a polyether sulfone, a polyphenylene sulfide, a polyether ketone, a polyether ether ketone, an ABS, a polystyrene, a polybutadiene, a poly(acrylate), a poly(alkylacrylate), a polyacrylonitrile, a polyacetal, a polycarbonate, a polyphenylene ether, an ethylene-vinyl acetate copolymer, a polyvinyl acetate, a liquid crystal polymer, an aromatic polyester, an ethylene-tetrafluoroethylene copolymer
- the present invention provides an article comprising a polymer-organoclay composite composition (a) a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, the organic layers comprising a quaternary organic cation; and (b) a polyetherimide composition, wherein the polymer-organoclay composite composition is characterized by a percent exfoliation_of at least 10 percent.
- Suitable polyetherimide compositions include ULTEM polyetherimide available from GE Plastics.
- the present invention provides a method of making a polymer-organoclay composite composition
- a polymer-organoclay composite composition comprising melt mixing in an extruder, a quaternary organoclay composition comprising alternating inorganic silicate layers and organic layers, said organic layers comprising a quaternary organic cation, with a polyetherimide composition comprising at least one polyetherimide and at least one additional polymer selected from the group consisting of polyamides, polyesters, polyarylene sulfides, polyarylene ethers, polyether sulfones, polyether ketones, polyether ether ketones, polyphenylenes, and polycarbonates; said melt mixing being carried out at a temperature in a range between about 300° C. and about 450° C.
- the quaternary organic cation has structure X. In another embodiment, the quaternary organic cation has structure XXV. In another embodiment, the quaternary organic cation has structure XXVI. In yet another embodiment, the quaternary organic cation has structure XXXIII.
- the present invention provides methodology for the preparation of polymer-organoclay composite compositions using in situ polymerization techniques to create a polymeric resin in the presence of an organoclay composition.
- the methodology developed presents various advantages, among them intimate contact between the organoclay composition and the nascent polymeric resin.
- the present invention provides a method of making a polymer-organoclay composite composition, said method comprising (a) contacting under condensation polymerization conditions a first monomer, a second monomer, a solvent, and an organoclay composition, said organoclay composition comprising alternating inorganic silicate layers and organic layers, to provide a first polymerization reaction mixture, wherein one of said first monomer and second monomers is a diamine and the other is a dianhydride; (b) carrying out a stoichiometry verification step on the first polymerization reaction mixture; (c) optionally adding additional reactant to the first polymerization reaction mixture to provide a second polymerization reaction mixture; and (d) removing solvent from the first polymerization reaction mixture or the second polymerization reaction mixture to provide a first polymer-organoclay composite composition comprising a polymer component and an organoclay component wherein the organoclay component is at least 10% exfoliated.
- the polymer component is a polymer component
- the polymerization is carried out in the presence of a catalyst, for example sodium phenyl phosphinate (SPP).
- a catalyst for example sodium phenyl phosphinate (SPP).
- the first monomer is a dianhydride and the second monomer is a diamine.
- Suitable diamines and dianhydrides include those disclosed herein, for example BPADA and metaphenylene diamine.
- Suitable solvents include aromatic solvents such as orthodichorobenzene, toluene, xylene, chlorobenzene, and combinations of the foregoing solvents.
- the organoclay composition can be any of the organoclay compositions disclosed herein.
- the verification of stoichiometry step may be carried out using any analytical technique suitable for determining accurately the ratio of the first monomer to the second monomer in the first reaction mixture.
- the ratio of the first monomer to the second monomer in the first reaction mixture may be determined by infrared analysis of a film prepared from an aliquot sample take from the first reaction mixture as described in the experimental section of the present disclosure.
- the ratio of the first monomer to the second monomer in the first reaction mixture may be determined by art recognized techniques such as high performance liquid chromatography (HPLC), Nuclear Magnetic Resonance (NMR), and end-group titration.
- the verification of stoichiometry step is important since careful control of the reaction stoichiometry must be exercised in order to achieve one or more target characteristics of the product polymer-organoclay composite composition.
- the stoichiometry verification step comprises determining an amine to anhydride ratio.
- additional monomer can be added.
- the verification of stoichiometry step can signal the need for the addition of another reagent such as a chain stopper.
- additional reactant is added to the first polymerization reaction mixture, it is deemed to constitute a second polymerization reaction mixture which may be further reacted by heating, for example.
- solvent is removed to provide a first polymer-organoclay composite composition
- a first polymer-organoclay composite composition comprising a polymer component and an organoclay component wherein the organoclay component is at least 10% exfoliated.
- Solvent removal may be effected by art recognized techniques such as distillation, filtration, antisolvent precipitation followed by filtration and the like.
- removing the solvent from the first polymerization reaction mixture or the second polymerization reaction mixture is carried out using a devolatilizing extruder, a wiped film evaporator, or a combination thereof.
- the first polymer-organoclay composite composition is further subjected to a step of melt mixing at a temperature in a range between about 300° C. and about 450° C. In certain embodiments such melt mixing further enhances the degree of exfoliation of the organoclay component of the polymer-organoclay composite composition.
- contacting under condensation polymerization conditions comprises heating at a temperature greater than 100° C. In an alternate embodiment, contacting under condensation polymerization conditions comprises heating at a temperature less than 100° C. In another embodiment, contacting under condensation polymerization conditions comprises heating in the presence of a solvent and a catalyst at a temperature greater than 100° C. In an alternate embodiment, contacting under condensation polymerization conditions comprises heating in the presence of a solvent and a catalyst at a temperature less than 100° C.
- the first monomer is a dianhydride having structure XL
- R 11 and R 12 are independently at each occurrence a halogen atom, a C 1 -C 20 aliphatic radical, a C 5 -C 20 cycloaliphatic radical, or a C 2 -C 20 aromatic radical; and W is a bond, a divalent C 1 -C 20 aliphatic radical, a divalent C 5 -C 20 cycloaliphatic radical, a divalent C 2 -C 20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO 2 linking group, or a Se linking group.
- the dianhydride XL is selected from the group consisting of bisphenol A dianhydride (BPADA), 4,4′-oxydiphthalic anhydride (4,4′-ODPA), 3,4′-oxydiphthalic anhydride (3,4′-ODPA), 3,3′-oxydiphthalic anhydride (3,3′-ODPA), 4,4′-biphenyl dianhydride, 3,4′-biphenyl dianhydride, combinations thereof.
- BPADA bisphenol A dianhydride
- 4,4′-ODPA 4,4′-oxydiphthalic anhydride
- 3,4′-ODPA 3,4′-oxydiphthalic anhydride
- 3,3′-oxydiphthalic anhydride 3,3′-ODPA
- 4,4′-biphenyl dianhydride 3,4′-biphenyl dianhydride, combinations thereof.
- the dianhydride employed is any of the dianhydrides disclosed herein.
- the second monomer is a diamine selected from any of the diamines disclosed herein, for example meta-phenylenediamine.
- the second monomer is an aromatic diamine.
- the aromatic diamine is selected from the group consisting of metaphenylene diamine, paraphenylene diamine, 4,4′-diaminodiphenyl sulfone, and 4,4′-oxydianiline.
- the organoclay composition comprises a quaternary organic cation.
- the quaternary organic cation has structure XXXIX
- Organoclay compositions comprising quaternary organic cations XXXIX are in certain instances commercially available. Alternatively, organoclay composition comprising quaternary organic cations XXXIX may be prepared using techniques disclosed herein.
- the quaternary organic cation is selected from the group consisting of decyl trimethyl ammonium cation, dodecyl trimethyl ammonium cation, tetradecyl trimethyl ammonium cation, hexadecyl trimethyl ammonium cation, octadecyl trimethyl ammonium cation, and combinations thereof.
- the organoclay composition comprises a non-quaternary organic cation, for example a protonated aromatic amine.
- the organoclay composition employed comprises alternating inorganic silicate layers and organic layers.
- the inorganic silicate layers may be derived from inorganic clay materials.
- the inorganic silicate layers are derived from an inorganic clay selected from the group consisting of kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasilylic mica, sodium taeniolite, muscovite, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite, and combinations thereof.
- the present invention provides a method of making a polymer-organoclay composite composition comprising (a) contacting a dianhydride with a diamine in a solvent at a temperature in a range between about 105° C. and about 250° C.
- the method further comprises a step of melt mixing the first polymer-organoclay composition at a temperature in a range between about 300° C. and about 450° C.
- the present invention provides a method of making a polyetherimide-organoclay composite composition
- a method of making a polyetherimide-organoclay composite composition comprising (a) contacting bisphenol A dianhydride (BPADA) with a diamine in orthodichlorobenzene at a temperature in a range between about 125° C. and about 250° C.
- BPADA bisphenol A dianhydride
- an organoclay composition comprising alternating inorganic silicate layers and organic layers, to provide a first polymerization reaction mixture; (b) determining an amine to anhydride ratio in the first polymerization reaction mixture; (c) optionally adding additional dianhydride or diamine to the first polymerization reaction mixture to provide a second polymerization reaction mixture; and (d) removing orthodichlorobenzene from the first polymerization reaction mixture or the second polymerization reaction mixture using a devolatilizing extruder to provide a first polymer-organoclay composite composition comprising a polymer component and an organoclay component wherein the organoclay component is at least 10% exfoliated.
- the organoclay composition has structure X.
- the present invention provides a method of making a polyetherimide-organoclay composite composition
- a method of making a polyetherimide-organoclay composite composition comprising (a) contacting 4,4′-oxydiphthalic anhydride (4,4′-ODPA) with a diamine in orthodichlorobenzene at a temperature in a range between about 125° C. and about 250° C.
- organoclay composition comprising alternating inorganic silicate layers and organic layers, to provide a first polymerization reaction mixture; (b) determining an amine to anhydride ratio in the first polymerization reaction mixture; (c) optionally adding additional dianhydride or diamine to the first polymerization reaction mixture to provide a second polymerization reaction mixture; and (d) removing orthodichlorobenzene from the first polymerization reaction mixture or the second polymerization reaction mixture using a devolatilizing extruder to provide a first polymer-organoclay composite composition comprising a polymer component and an organoclay component wherein the organoclay component is at least 10% exfoliated.
- Bisphenol A dianahydride (BPADA, CAS No. 38103-06-9) (97.7% purity) was obtained from GE Plastics.
- 4,4′-Oxydiphthalicanhydride (ODPA, CAS No. 1823-59-2) (99% purity) was from Chriskev Company, Lenexa, Kans., USA.
- the organoclay compositions were made with Kunipia F montmorillonite unless indicated otherwise. See for example those organoclay compositions made with Nanocor PGN.
- Kunipia F montmorillonite was purchased from Kunimine Industries Co. The manufacturer's reported cation exchange capacity (CEC) is 115 meq/100 g.
- Un-dried Kunipia F contains 8 wt % of moisture at room temperature, and a sodium analysis of an un-dried Kunipia F sample gave a sodium content of 23,850 ( ⁇ 500) ppm, which indicated a CEC of 103.7 meq/100 g for un-dried sample.
- a cation exchange capacity value of 100 meq/100 g was used for all calculations and material preparations.
- the aspect ratio for Kunipia F montmorillonite is 320 (average), 80 (minimum), 1120 (maximum). Comparable montmorillonites may be obtained from Nanocor. Products PGV and PGN which have aspect ratios of 150-200 and 300-500 nm respectively.
- the cation exchange capacities of PGV and PGN clays are 145 (+10%) and 120 (+10%) meq/100 g respectively.
- Sonication of organically modified montmorillonites in solvent was performed using a 450 W model of Branson Sonifier 450 with a 0.5′′ diameter solid probe.
- a 1500 W model of Autotune Series High Intensity Ultrsonic Processor from Sonics & Materials inc. was used.
- TGA measurements were performed on a Perkin Elmer TGA 7 using Pyris software. A temperature ramp spanning 25 to 900° C. at a rate of 20° C./minute was used for all ramped samples. Isothermal runs were performed at 400° C. to examine thermal stability at the target processing/extrusion temperature. Thermal stabilities are reported as the onset temperature of mass loss and % weight retention at 30 minutes for isothermal runs.
- TMA Thermal Mechanical Analysis
- TEM Transmission Electron Microscopy
- X-ray Diffraction (XRD) (Low angle XRD) measurements were carried out on a Bruker D8 advance diffractometer using ⁇ - ⁇ geometry. Ni-filtered Cu K ⁇ radiation was used with a M-Braun PSD-50m position-sensitive-detector and an incident slit of 0.6 mm. The scanning range was from 1.4-25 degrees 2 ⁇ .
- Percent Exfoliation is defined as follows. Inorganic fillers have a volumetric effect on the Coefficient of Thermal Expansion (CTE). For each volume % of filler incorporated into a polymer matrix, there is a corresponding % reduction in CTE. Therefore, when an organoclay composition is added to a polymeric resin, any decrease in CTE above the volumetric effect is directly related to the exfoliation of the organoclay composition in the polymer matrix. A percent exfoliation can be calculated as the ratio of the normalized CTE (CTE due to volumetric filling) to the experimentally measured CTE.
- CTE Coefficient of Thermal Expansion
- the product phosphonium compound ((3-Aminophenyl)triphenylphosphonium Iodide) separated from solution as a yellow-orange solid. Excessive refluxing was avoided to prevent discoloration of the product phosphonium compound.
- the progress of the reaction was monitored using thin layer chromatography (TLC) with a 50/50 hexane/ethyl acetate developing solution. After the reflux, the product was filtered. The product 1 was reslurried with hot toluene, and stirred for 15 minutes. The solution was then filtered and rinsed with additional toluene/xylene. After drying in a 150° C.
- a 3 L 3-necked round-bottomed flask was equipped with a condenser, mechanical stirrer, and an addition funnel.
- the flask was charged with 4-(4-cumylphenoxy)-phthalonitrile (278 g, 0.82 mole) and acetic acid (1.6 L).
- the addition funnel was filled with 70% sulfuric acid (670 mL). The solution was heated to 120° C., and then sulfuric was added drop-wise into the reaction mixture over 2 hours. The resulting mixture was refluxed overnight (12 hours).
- the reaction mixture was cooled to room temperature, and poured into an ice-water mixture (1 kg).
- the product was extracted with ethyl acetate (3 ⁇ 300 mL).
- a 500 mL glass reaction vessel fitted with a mechanical stirrer, nitrogen inlet and gas outlet was charged with 66.27 g (0.1848 mol) 4-(4-cumyl)phenyoxy-phthalic anhydride 3 and 88.97 g (0.1848 mol) 3-aminophenyl)triphenylphosphonium Iodide (mATPP iodide) 1.
- the vessel was then placed in a heating mantle enclosure and heated to about 300° C. to produce a molten reaction mixture. After stirring for about three minutes, vacuum was applied to remove water formed as a byproduct.
- reagents m-aminotetraphenylphosphonium iodide, 22.14 g (0.046 mol), and 4-chlorophthalic anhydride, 8.40 g (0.046) were weighed out and added to a 250 ml round bottom flask equipped with a Dean-Stark condenser and dissolved in 150 mL of o-dichlorobenzene. The contents were heated to reflux and the water was removed by azeotropic distillation and a nitrogen purge. After 4 h at reflux, 10.78 g of sodium cumylphenolate (0.046 mol) was added and the contents stirred and heated for an additional 4 h.
- the diamine (4,4′-diaminodiphenyl sulfone (DDS) or alpha-methyl styrene dimmer diamine (AMSDDA) (0.3 mol)) was added to a round bottom flask fitted with a stirrer, nitrogen inlet, Dean-Stark apparatus and a condenser. About 0.1 mole (18.26 g) of 4-chlorophthalic anhydride was added to the diamine along with about 300 ml of ortho-dichlorobenzene. The round bottom flask was heated to about 190-200° C. for 4 hours under nitrogen with removal of water. The reaction mixture was then cooled to room temperature and added with stirring to about 1500 ml of hexane. The product monochlorophalimide was collected and dried in an oven at 100° C.
- DDS diaminodiphenyl sulfone
- AMSDDA alpha-methyl styrene dimmer diamine
- the monochloroimide (0.1 mol) was added to a flask fitted with a stirrer, nitrogen inlet, and condenser.
- the reaction mixture was then cooled to room temperature and stirred in about 1000 ml of dichloromethane and water (1000 ml). The layers were separated and the organic layer was washed until it free of nickel chloride color.
- the solvent was removed under vacuum and toluene was added to the sticky residue and subsequently the toluene was removed under reduced pressure. The toluene addition and removal was repeated until a solid product was obtained.
- the final product was then dried under vacuum.
- the structures of products 9 and 10 were confirmed by 1 H-NMR.
- the dianhydride (oxydiphtahlic anhydride (0.1 mol)), 3-chloroaniline (26.77 g, 0.21 mol), and ortho-dichorobenzene (300 ml) were charged to a reaction flask fitted with a stirrer, nitrogen inlet, Dean-Stark apparatus and condenser.
- the reaction mixture was heated to about 190-200° C. for 4 hours under nitrogen with removal of water.
- the reaction mixture was then cooled to room temperature and added to about 1500 ml of methanol.
- the intermediate bis(chloro-imide) was then filtered and dried in an oven at 100° C. to constant weight.
- the bis(chloro-imide) was converted to the bis(phosphonium imide) 11 as in Examples 9 and 10.
- the diamine (tricyclododecyl diamine (0.3 mol)) phthalic anhydride (0.1 mol) and orthodichorobenzene (300 ml) were charged to a reaction flask fitted with a stirrer, nitrogen inlet, Dean-Stark and condenser. The mixture was heated to about 190-200° C. for 4 hours under nitrogen with removal of water. The reaction mixture was then cooled to room temperature and stirred into about 1500 ml of hexane/methanol to afford the intermediate monophthalimide as a mixture of isomers which was dried at 100° C. to constant weight.
- the monophthalimide (0.1 mol), 4-chlorophthalic anhydride (0.1 mol) and orthodichorobenzene (300 ml) were charged to flask equipped as above. The mixture was heated to about 190-200° C. for 4 hours under nitrogen with removal of water. The reaction mixture was then cooled to room temperature and stirred into about 1500 ml of hexane/methanol to afford the intermediate monophthalimide-monochlorophthalimide as a mixture of isomers which was dried at 100° C. to constant weight.
- the monophthalimide-monochlorophthalimide intermediate was reacted with triphenylphospine in the presence of nickel(II) chloride as described in Example 8 to afford the product bisimide-monophosphonium salt 12 as a mixture of isomers.
- phosphonium salt 1 (Example 1, 17.36 g, 0.036 mol) and methanol (900 ml) and heated to about 64° C.
- sodium montmorillonite clay Na-MMT/Kunipia F clay, 30.00 g, 0.030 mol equivalents
- Na-MMT/Kunipia F clay 30.00 g, 0.030 mol equivalents
- the mixture was blended vigorously for about 10 minutes and then more slowly for an additional 20 minutes. The temperature was about 65° C. After about 30 minutes of blending, the mixture was filtered using a large fine fritted funnel. The solid clay was re-slurried in hot (80° C.) water, stirred for 15 minutes and filtered. The solid clay was then slurried in hot (64° C.) methanol and then filtered. The purified clay was dried under vacuum at room temperature until it could be ground into a powder. The moist powder was dried at 150° C. for about 12 hours under vacuum and ground again to obtain about 30 g of dry organoclay composition clay in 76% yield.
- the clay was then filtered, re-slurried with 2500 mL of deionized water and stirred at 80° C. for 15 minutes. After filtering the clay, an acetonitrile wash was also performed followed by a final filtration.
- the modified clay was dried for 24 hours under a 25° C. vacuum until it could be blended to a powder. The modified clay further in a 150° C. vacuum for 12 hours, the clay was blended again to give the organoclay composition comprising cation 14 as fine powder in about 84% yield.
- Organoclay Compositions Comprising Phosphonium Cation 15 or 16
- organoclay compositions comprising organophosphonium cation 15 (Example 15, Cumyl-MMT) or 16 (Example 16) were prepared as in Example 14.
- An inorganic clay (sodium montmorillonite, “Na-MMT”, available from Southern Clay, Inc.) was slurried in 75 volumes deionized water (“MilliQ water”) with respect to the weight of clay and stirred at room temperature (22-25° C.) for 1 hour and then at 90-95° C. for 1 hour.
- the solution of organophosphonium salt in methanol or acetonitrile was then added protionwise to the slurry of the inorganic clay the reaction mass was stirred for 18-20 hrs at 65-95° C.
- the crude organoclay composition was filtered and washed until the washing were free of halide and then dried at 125-150° C. to constant weight.
- Organoclay compositions comprising monophosphonium bisimide organophosphonium cations are gathered in Table 2 along with d-spacing data determined by x-ray diffraction (XRD).
- Organoclay compositions comprising diphosphonium bisimide organophosphonium cations are gathered in Table 3 along with d-spacing data determined by x-ray diffraction (XRD).
- Organoclay compositions comprising amino-phosphonium monoimide organophosphonium cations are gathered in Table 4 along with d-spacing data determined by x-ray diffraction (XRD).
- the mixture was heated to reflux and 200 ml of a veratrole-water mixture was removed over a 12 h period. Then another 400 mL of veratrole was distilled from the reaction vessel over a 3 h period. The reaction mixture was then cooled to 80° C. and poured into a high speed blender containing 2 L of methanol. The resulting solid polymer was filtered and dried at 250° C. in a vacuum oven for 15 hours. The product polymer-organoclay composite composition (253 g) was obtained in 75% yield. The formulated degree of polymerization was 35. The formulated weight percent silicate was 7%.
- the product polymer-organoclay composite compositions were also characterized by x-ray diffraction (XRD), transmission electron microscopy. In addition, coefficients of thermal expansion (CTE) were determined.
- XRD x-ray diffraction
- CTE coefficients of thermal expansion
- the inorganic clay used to prepare the organoclay compositions employed (Na-MMT, Southern Clays, USA) exhibited a d-spacing of 9.7 angstroms.
- the polyetherimide employed had an initial weight average molecular weight (Mw) of 44,965 grams per mole and an initial number average molecular weight of 19,200 grams per mole, and exhibited a CTE of about 62.1 (ppm).
- Polymer-Organoclay Composite Compositions Prepared Via In situ Polymerization Comprising a Polymeric Resin Comprising Structural Units Derived from DDS and BPADA or ODPA
- Polymer-organoclay composite compositions 38-43 and 46-51 were prepared as described in the following Example (Example 43).
- the organoclay composition comprising cation 14 (BPADA-mATPP-MMT), 9.05 g and 59.85 g of oxydiphthalic anhydride (ODPA) was added to 219 ml of orthodichorobenzene (oDCB) and 146 mL of veratrole. The mixture was mixed with a mechanical stirrer for 2 hours to dissolve the ODPA. The vessel was then immersed in a bath sonicator and sonicated until a fine dispersion of the clay was obtained.
- BPADA-mATPP-MMT BPADA-mATPP-MMT
- ODPA oxydiphthalic anhydride
- oDCB orthodichorobenzene
- veratrole veratrole
- the Flask was then equipped with an overhead stirrer and a Dean-Stark trap and 46.33 g of 4,4′-diaminodiphenyl sulfone (DDS) and 0.08913 g of aniline were added. 60 mL of oDCB and 40 mL of veratrole was used to rinse the DDS into the vessel. The mixture was stirred and heated slowly to reflux over three hours and the water removed by azeotropic distillation. After heating at reflux for 18 h, a dispersion of fine powder was obtained.
- DDS 4,4′-diaminodiphenyl sulfone
- the dispersion was added to a larger volume of methanol, filtered and dried under vacuum at 180 C
- the resulting dried powder was then transferred to a Haake melt mixer and mixed at 390 C and 50 rpm for 60 min. Samples were removed at 5 min intervals.
- the 15 minute sample was pressed into a film between two sheets of Teflon lined foil at 760 F.
- the pressed film sample was then submitted for analysis by Thermal Mechanical Analysis and the CTE measured over the range 30 to 200 C.
- Polymer-organoclay composite compositions 44-45 were prepared as follows.
- a SILVERSON mixer (Lab in line mixer assembly model L4R-PA, square hole high shear screen, pumping at ⁇ 600 mL/min) was used to mix the organoclay with solvent.
- 450 mL orthodichlorobenzene (oDCB) was pumped through the SILVERSON mixer.
- the organoclay composition comprising cation 14 (BPADA-mATPP-MMT), 13.1 g was added slowly to the recirculating oDCB.
- the mixture was run through the SILVERSON high shear mixer at 6000 rpm for 45 minutes in recirculation mode. The mixture was then transferred to a 1 L three-necked flask.
- the flask was then equipped with an overhead stirrer and a Dean-Stark trap. 74.2 g of bisphenol A dianhydride (BPADA) was added and the flask was heated to 100° C. to dissolve the dianhydride. 33.90 g of 4,4′-diaminodiphenyl sulfone (DDS) was then added and 20 mL of oDCB was used to rinse the DDS into the vessel. The mixture was stirred and heated slowly to reflux and the water by-product was removed by azeotropic distillation. After heating at reflux for 3.5 h, the heat was removed and the reaction mixture was allowed to cool to room temperature.
- BPADA bisphenol A dianhydride
- DDS 4,4′-diaminodiphenyl sulfone
- the resulting viscous mixture was transferred to a Haake melt mixer and mixed at 390 C and 50 rpm for 60 min. Samples were removed at 5 minute intervals. The 15 minute sample was pressed into a film between two sheets of Teflon lined foil at 760 F. The pressed film sample was then submitted for analysis by Thermal Mechanical Analysis and the CTE measured over the range 30 to 200° C.
- a organoclay composition comprising cation 15 was sonicated in veratole.
- the mixture subjected to sonication comprised about 2.7% organoclay composition in 500 mL of veratrole.
- Sonicated was carried out in a 1000 mL round-bottom flask submerged in a water bath using a Branson 450 W Sonifier fitted with a 1 ⁇ 2′′ sonic probe at ⁇ 40% power output for ⁇ 16 hrs.
- a total of five essentially identical organoclay composition-solvent batches were sonicated and then combined.
- To the combined batches of the sonicated organoclay composition was added a 20 weight percent solution of the BPADA-DDS polyetherimide in veratrole and the mixture was thoroughly mixed.
- This mixture was then added to a blender containing methanol.
- the resultant solid powder was filtered and dried at 220° C. under vacuum, and then blended with an amount of a second polyetherimide, ODPA-DDS polyetherimide, sufficient to give a 69:31 ratio of the BPADA-DDS polyetherimide and ODPA-DDS polyetherimide polyetherimides.
- the resultant mixture was extruded into film through a 3′′ film die.
- the resulting film had a nanosilicate loading of 7%, a machine direction CTE of 33.0 ppm/° C., and a T g of 255° C. (see FIG. 1 for TEM image).
- a control film containing the same ratio of BPADA-DDS polyetherimide to ODPA-DDS polyetherimide with no clay exhibited a machine direction CTE of 48.5 ppm/° C. and a T g of 262° C.
- a film was also extruded with an BPADA-DDS polyetherimide: to ODPA-DDS polyetherimide of 60:40 and a nanosilicate loading of 7%. That film had a machine direction CTE of 28.7 ppm/° C. and a T g of 266° C.
- reaction mixture was cooled back to room temperature.
- Palladium on carbon (10 wt % Pd, 25 g, 0.025 mole) was added to the reaction mixture followed by ammonium formate (350 g, 5.463 mole). Internal temperature of the solution of reaction mixture was kept below 55° C. using cold water during the reaction.
- BAPP 4,4′-(4,4′-Isopropylidenediphenyl-1,1′-diyldioxy)dianiline
- triphenylpyrylium tetrafluoroborate 40.5 g, 0.102 mole
- ethanol 400 mL
- Table 7 provides yield and characterization data for the pyridinium salts 27, 28, 30 and 31.
- the modified montmorillonite was collected by filtration, and washed with hot water (2 L, 80° C.) to remove inorganic salt by-product NaBF 4 .
- the modified clay (organoclay composition) was further purified by re-dispersing it in acetonitrile (2 L) at 60° C., followed by filtration to remove the any excess pyridinium salt.
- the purified clay was dried under vacuum for 24 hours at 150° C. and was milled to give a fine powder (50.3 g, 80% yield).
- a solution of organic modifier was prepared by stirring 352 g of CumylPhenoxy-TPPy-BF4 30 modifier into 7 liters acetonitrile and heating to 80° C. until all the organic salt dissolved. The salt solution was added over a period of about 10 min with constant stirring of montmorillonite at 80° C.
- the modified clay mixture was gravity-transferred to the filtration centrifuge that was fitted with a one-micron filtration bag. The centrifuge was run at both low and high speeds to give a firm cake of modified clay.
- the modified clay was washed by placing the clay back in Vessel 1 with 47 liters of water and stirring at 80° C. for 15 minutes.
- the modified clay mixture was again filtered.
- the modified clay was washed again by placing the clay back in Vessel 1 with 15 liters of acetonitrile and stirring at 80° C.
- the clay was re-filtered to remove unexchanged organic modifier.
- the clay in the centrifuge basket was rinsed briefly with methanol to aid in drying uniformity.
- the modified clay was dried overnight in either a low-temperature vacuum oven (100° C.) or in the centrifuge with a nitrogen purge.
- the clay was milled in a Merlin mixer to give a powder. Further drying in a 150° C. vacuum oven followed by further blending gave a very fine powder of low ( ⁇ 2%) moisture content in about 70% yield.
- Characterization data for a series of organoclay compositions is provided in Table 8.
- the heading “Exp wt % of C” stands for Experimentally determined weight percentage of carbon present in the organoclay composition”.
- the heading “Exp wt % of H” stands for Experimentally determined weight percentage of hydrogen present in the organoclay composition”, etc.
- the heading “Calc wt % C” stands for “Calculated weight percent carbon present in the organoclay composition”, etc.
- organoclay compositions were further characterized in terms of “d-spacing”, and “percent of exchange” of inorganic ions by organic ions using the carbon combustion analysis data, the hydrogen combustion analysis data, and the sodium ion concentration data.
- the data are presented in Table 9 and while the degree of exchange indicated varies somewhat according to the method of analysis used in the calculation, all three methods indicate extensive exchange of sodium ion by the pyridinium cation.
- ODPA-DDS-Aniline Polyetherimide A typical procedure for synthesis of the ODPA-DDS polyetherimide is as follows. ODPA (15.18 kg) was charged to a stirred glass lined reactor with 123.65 kilograms (kg) of oDCB with 0.35 kg aniline. The reactor was heated to 180° C. using oil heating and 8 kg of oDCB was removed. The reactor was cooled to about 120° C. and 11.215 kg DDS added with stirring. The oil temperature was raised to 155° C. over 210 minutes, and the slurry temperature reached about 146° C. Water began to evolve; a nitrogen sweep was used to help remove water from the reactor. The oil temperature was raised to 171° C.
- the reaction temperature increased to about 166° C. as water evolved.
- the slurry was still easily stirred.
- the oil temperature was raised to 186° C. and the reaction temperature increased to about 177° C. over the next 25 minutes.
- the DDS incorporation was judged sufficient to further increase the oil temperature to 195° C. giving a reaction slurry temperature of 179° C.
- Over the next hour 45 kg of condensate was removed. Heat was reduced and the reaction cooled to 50° C. No stickiness of the polymer was observed.
- the precipitated polyetherimide was removed from solution by centrifugation at about 12° C. using a 5 micrometer centrifuge bag. The polymer was dried at 150° C. in a double cone dryer. The resultant powder passed through a 2 mm sieve.
- a 3 inch wide and 4 mil thick film was extruded from a resin composition consisting of 31% by weight of a polymer-organoclay composite composition prepared in Example 63 (ODPA-DDS polyetherimide containing 7 wt % Layered Silicate TPPy-MMT) and 69% by weight of the polymer-organoclay composite composition prepared in Example 62 (BPADA-DDS polyetherimide containing 7 wt % layered silicate TPPy-MMT).
- a 16 mm PRISM extruder equipped with a venting/finishing screw and a 3-inch film die was used. The resin composition was fed at rate of about 0.5 lb per hour.
- the screw speed was set at 200 rpm, barrel temperature at 370° C., and film die temperature at 380° C.
- the die pressure was about 1500 psi, during the film extrusion.
- a control film of similar composition but lacking the organoclay was extruded on the same extruder system and the die pressure was measured and found to be only about 900 psi.
- GPC analysis of the extruded film indicated that the polymer built molecular weight during the film extrusion process. Although the extruded film was creasable, the TEM images of the film indicated relatively poor dispersion of the TPPy-MMT organoclay within the polyimide matrix. The relatively poor dispersion of the organoclay was reflected in the CTE results wherein only 18% CTE reduction was observed relative to the unfilled control sample. This was equivalent to a relatively modest 2.6% reduction in CTE per wt % of silicate.
- Polymer-Organoclay Composite Compositions Comprising a Resin Blend of 31 wt % of BPADA-DDS Polyetherimide and 69 wt % of ODPA-DDS Polyetherimide and Films Made Therefrom
- a series of polymer-organoclay composite compositions comprising a polyetherimide (ODPA-DDS polyetherimide or BPADA-DDS polyetherimide) and an organoclay composition (CumylPhenoxy-TPPy-MMT) were prepared and are shown in Table 11 below.
- the diamine was DDS and the endcapping agent was aniline.
- the amount of endcapping agent was adjusted according to a “targeted” molecular weight. Two molecular weight targets, 25 Kg/mol (“Lo”) and 30 Kg/mol (“Hi”), were prepared for each resin.
- a 16 mm Prism extruder with venting/finishing screw equipped with a 3-inch film die was used. The combinations were fed at rate of 0.5 lb per hour. The screw was set at 200 RPM, barrel temperature at 380° C. and film die temperature at 390° C. The die pressure was about 1200 psi. Data for the extruded films is gathered in Table 12.
- Example Polyimide Blend Compositions (Kg/mol) (Kg/mol) (Kg/mol) (Kg/mol) (ppm/° C.) 69 31 wt % ODPA- 69 wt % BPADA- 46.9 18.9 49.5 20.2 nd* DDS DDS polyetherimide - polyetherimide - Lo Lo 70 31 wt % ODPA- 69 wt % BPADA- 65.9 22.8 56.9 21.9 nd DDS DDS polyetherimide - polyetherimide - Hi Lo 71 31 wt % ODPA- 69 wt % BPADA- 46.3 19.1 51.8 21.2 nd DDS DDS polyetherimide - polyetherimide - Lo Hi 72 31 wt % ODPA- 69 wt % BPADA- 57.8 20.8 61.0 23.6 44 DDS DDS polyetherimide - polyetherimide - Hi Hi Control 31 wt %
- Example 69 the film prepared from a polymer-organoclay composite composition formulation of low molecular weight ODPA-DDS polyetherimide resin and low molecular weight BPADA-DDS polyetherimide resin has a post-extrusion molecular weight comparable to a control blend comprising no organoclay. However, while the control is ductile, the film sample of Example 69 was brittle.
- Films comprising a polymer-organoclay composite composition such as those illustrated in Examples 69-72 are at times referred to as “nanocomposite films” owing to the very high level of exfoliation of the organoclay composition containing in the polymer-organoclay composite composition used to prepare the films.
- reaction was cooled to room temperature, and water (400 mL) was added to the reaction mixture and the desired product precipitated out of solution as a cream white solid.
- water 400 mL
- desired product precipitated out of solution as a cream white solid.
- the product was further purified by re-crystallization isopropanol (400 mL) to give the desired product as a white crystalline solid (25 g, 87% yield).
- reaction progress was monitored using TLC with a 90/10 methylene chloride/methanol developing solution.
- the product was further purified by flash chromatography using silica gel 60 (500 g) and methylene chloride with 5% methanol as solvent. A red impurity was eluted first followed by the desired phosphonium salt 32 (40 g, 82% yield) which was isolated as a cream colored powder after removal of solvent.
- PhEK-MMT the Organoclay Composition Derived from 4-(4-Benzoyl-phenoxy)-phenyl-triphenylphosphonium iodide and Sodium Montmorillonite
- a 5 L round-bottom flask equipped with a mechanical stirrer was charged with sodium montmorillonite (30 g, 0.03 mole) and deionized water (2.5 L). The solution was stirred and heated at 85° C. until the sodium montmorillonite was well dispersed.
- a solution of phosphonium salt 32 (22.8 g, 0.034 mole) in acetonitrile (600 mL) was warmed to about 60° C. and was then added to the suspension of sodium montmorillonite over 10 min. After the addition of the salt solution, the reaction mixture was stirred at 85° C. for about 3 hours.
- the organoclay composition (also at times referred to as a modified montmorillonite, or simply “the modified clay”) was collected by filtration, and washed with hot water (2 L, 80° C.) to remove inorganic salt impurities and the sodium iodide by-product of the exchange reaction.
- the modified clay was further purified by re-dispersing in acetonitrile (2 L) at 60° C., followed by filtration to remove any excess phosphonium salt.
- the purified clay was dried under vacuum for 24 hours at 150° C. and was milled to give PhEK-MMT as a fine powder (40 g, 72% yield)
- a 500 Ml Beaker was charged with 200 mL of water and 0.7183 g of bis-4-(triphenylphosphonium) benzophenone dichloride. The mixture was heated to reflux for 2 h. After cooling to room temperature the organocaly was isolated by centrifugation, washed with two 200 mL portions of deionized water and recollected by centrifugation.
- PEEK 450G resin was cryogenically ground with a 3 mm mesh.
- the resulting material had a mix of fine powder and larger granules.
- the ground material was passed through a 1 mm screen and the fine powder granules were collected. The grinding was necessary to feed the material through the small diameter 16 mm extruder, and to insure good mixing of the ground clay.
- the ground resin was blended with powdered PhEK-MMT (See Example 75 for preparation) in an amount corresponding to an inorganic silicate loading of 5%.
- PhEK-MMT See Example 75 for preparation
- two other organically modified clays were prepared as well (Examples 77 and 78).
- blends of the ground PEEK 450G resin were also prepared with the organoclay compositions Cumyl-MMT (Example 77) and TPP-MMT (Example 78).
- the preparation of Cumyl-MMT, an organoclay composition comprising organophosphonium cation 15 is given in Example 15 of this disclosure.
- TPP-MMT is an organoclay composition comprising silicate layers derived from sodium montmorillonite clay and a tetraphenyl phosphonium halide and can be prepared by methods disclosed herein.
- the amounts of organoclay composition and polymeric resin used in Examples 76-78 are given in Table 13. The formulations were mixed by placing both components in a plastic bag and shaking for several minutes.
- the pellets collected for each material at the low throughput (0.5 lb/hr) were compression molded to thin disks using a hot press.
- the disks were submitted for TEM analysis to determine the extent of dispersion. Results are gathered in Table 14.
- TEM Transmission electron microscopy
- Example 76 It is believed that the enhanced dispersion observed for the polymer-organoclay composite composition of Example 76 is due to the structural similarities between the polymeric resin used, PEEK 450G, and the organoclay composition used, PhEK-MMT.
- the PEEK 450G resin and the organoclay composition PhEK-MMT comprise 4-aryloxy substituted benzophenone moieties.
- Neither of the organoclay compositions employed in Examples 77 and 78 comprise a 4-aryloxy substituted benzophenone moiety.
- TEM Transmission electron microscopy
- TEM results for the TPP-MMT modified clay in PEEK (Example 78) likewise indicated relatively poor dispersion of the organoclay composition in the polymeric resin. Large tactoids of clay were visible in the transmission electron micrographs taken, which indicated that at least a portion of the organoclay composition did not exfoliate completely into the PEEK polymer matrix.
- polymer-organoclay composite compositions which are substantially free of polyetherimides may be prepared according to the method of the present invention by melt mixing a quaternary organoclay composition with a polymeric resin at a temperature in a range between about 300° C. and about 450° C.
- the data suggest that in order to attain high levels of exfoliation (>10% exfoliation) the polymeric resin and the organoclay composition should be melt mixed at greater shear than is typically provided in a low shear mixer such as a Haake mixer.
- compositions of 79-81 would have attained a % exfoliation of greater than 10% had the melt mixing been carried out in a higher shear environment such as a twin screw extruder operated at a temperature in a range between about 300° C. and about 450° C.
- organoclay composition methylene blue modified clay (4 wt % silica) prepared as above and 59.85 g of oxydiphthalic anhydride was added to 365 ml of oDCB and the vessel was immersed in a bath sonicator and heated until a fine dispersion of the clay that resisted settling was obtained. The Flask was then equipped with an overhead stirrer and a Dean-Stark trap and 46.35 g of DDS and 0.08978 g of aniline were added. 100 mL of oDCB was used to rinse the DDS into the vessel. The mixture was stirred and heated slowly to reflux over three hours and the water removed by azetropic distillation.
- organoclay composition methylene blue modified clay 4 wt % silica
- a series of polymer-organoclay composite compositions comprising polyetherimide were first prepared using one of the melt mixing, the in situ polymerization, or the solvent mixing techniques described herein. (See for example, Examples 27-29 which illustrate the in situ polymerization technique).
- the materials were obtained from the polymerization process as a large solid block of dried cake. The cake is broken into several ⁇ 1′′ pieces and the pieces were ground to a fine powder using a retsch mill and a 3 mm mesh screen.
- the fine powdered polymer-organoclay composite composition was then extruded alone or mixed with another powdered polymer-organoclay composite composition and extruded.
- the screw design provided for melting, mixing, devolatilizing, and conveying the powdered polymer-organoclay composite composition from the feed inlet to the film-forming die outlet of the extruder.
- a 3′′ (3 inch) or a 6′′ (6 inch) die was routinely used to convert the molten polyetherimide-containing polymer-organoclay composite composition into films.
- the powdered polymer-organoclay composite composition was first pelletized using the 16 mm Prism extruder with a venting/finishing screw and 3 mm pelletizing die.
- the organoclay composition-polymeric resin mixture (polymer powder blends) were “starve-fed” at rate of 1 lb per hour.
- the screw speed was set at 250 RPM, the barrel temperature at 385° C., and die temperature at 385° C.
- the pellets obtained from the finishing extrusion were dried overnight in a vacuum oven at 150° C. and were extruded to film using a Welex 11 ⁇ 4′′ single screw extruder with a 6′′ wide film die and barrier-type screw.
- the extruder screw was “starve-fed” at rate of 4 lb/hr and screw rotation speed of 25 RPM.
- the die gap was approximately 8 mils, and the extruded film was pulled with a film take-off unit at various speeds to obtain film of many different thicknesses.
- the molten resin was pulled by a set of rollers, the roll speed which could be adjusted to pull the film faster than the rate at which the molten polymer-organoclay composite composition exited the die, thereby thinning and orienting the product film.
- Circulating oil through the interior of the rollers allowed for maintenance of a specified temperature.
- the films were extruded using a chill casting process in which the rollers were configured in an “S wrap” configuration, where the film was wound around the middle and bottom rollers to allow sufficient time for cooling heat transfer.
- the film was then pulled by another set of rollers, the nip rolls, which put tension in the film, keeping the film in close contact with the front rollers.
- the film then passed through the nip rollers and was collected on a winder.
- Other conventional film handling equipment may also be used.
- Exemplary films comprising polyetherimide-containing polymer-organoclay composite compositions were prepared and the thermal expansion coefficients (CTE) for selected film samples were measured in the machine and transverse directions. Test results are gathered in Table 16.
- SILVERSON high shear mixer To a SILVERSON high shear mixer are added the imidazolium modified clay (14 g) and oDCB (450 mL) and the mixture is heated to 120° C. for 2 hours while maintaining vigorous mixing.
- the mixing system comprising the SILVERSON high shear mixer was equipped with a reservoir fitted with heat tape and a temperature controller. The contents of the reservoir were introduced into the bottom of the SILVERSON mixer. A recycle line further connected the SILVERSON mixer back to the reservoir. After cooling to room temperature, the reaction mixture is transferred to a 2 L three-necked round bottom flask equipped with overhead mechanical stirrer, dean-stark trap, and condenser. To this flask is added BPADA (74.2 g) and the mixture was stirred at 150° C.
- the targeted degree of polymerization was 30.
- Aniline was used as an end-capper.
- a 12 L round bottom flask was charged with DDS (280 g, 1.128 mole), CumylPhenoxy-TPPy-MMT (280 g) and veratrole (5.5 kg).
- the mixture was homogenized using a Fisher Scientific PowerGen rotor-stator homogenizer (manufactured by Omni International) fitted with a 32 mm saw-tooth tip running at 9000 RPM for 45 minutes.
- the resulting mixture was sonicated for 2 hours using a 1500 W model of Autotune Series High Intensity Ultrsonic Processor equipped with a 1-inch diameter solid probe at 70% setting. After sonication, the mixture became very thick and difficult to stir.
- a 10 gal reactor was charged with the dispersed clay mixture, DDS (458.8 g, 1.848 mole), BPADA (1600 g, 3.004 mole), aniline (11.68 g, 0.125 mole) and veratrole (4 kg).
- the reaction mixture was mechanically stirred and heated to 200° C. over a two-hour period, and was kept at this temperature for another 2 hours, and water distilled from the reaction mixture was collected.
- a SILVERSON mixer (Lab in line mixer assembly model L4R-PA, square hole high shear screen, pumping at ⁇ 600 mL/min equipped as in Example 95) was used to mix the organoclay with solvent. 270 mL ortho-dichlorobenzene (oDCB) and 180 mL of veratrole was heated to 80 C and pumped through the SILVERSON mixer. The organoclay composition comprising CLOISITE 30B (13.56 g) and Bisphenol A dianhydride (BPADA) (74.51 g) was added slowly to the recirculating solvent. The mixture was run through the SILVERSON high shear mixer at 6000 rpm for 45 minutes in recirculation mode. The solution temperature increased from 56 C to 79 C.
- the resulting solution was transparent indicating exfoliation of the organoclay mixture.
- the mixture was transferred to a 1 L three-necked flask. The Flask was then equipped with an overhead stirrer and a Dean-Stark trap and placed in an oil bath that was heated to 100° C. 33.88 g of 4,4′-diaminodiphenyl sulfone (DDS) was added. The mixture was stirred and heated to reflux. The water removed by azeotropic distillation. Phthalic anhydride (0.86 g) was added and allowed to react for 2 hours. A 10 g sample of the reaction mixture was the taken and the solvent was removed under nitrogen at 350° C.
- DDS 4,4′-diaminodiphenyl sulfone
- the residual polymer sample was pressed into a film and the infrared (IR) spectrum of the film was measured and the ratio of amine end-group to anhydride end-group was determined. From the IR spectrum it was found that the polymer sample contained 0.5 mole % excess anhydride. Using this information the reaction stoichiometry was adjusted by adding DDS (0.182 g) to correct for the excess anhydride content. The reaction mixture was then kept at 200° C. for an additional hour. A second 10 g sample or the reaction mixture was treated as above. From the IR spectrum it was found that the polymer sample contained 0.5 mole % excess anhydride. An additional 0.189 g of DDS was added to the reaction mixture and allowed to react for 1 hour.
- IR infrared
- a SILVERSON mixer (Lab in line mixer assembly model L4R-PA, square hole high shear screen, pumping at ⁇ 600 mL/min) was used to mix the organoclay with solvent. 270 mL ortho-dichlorobenzene (oDCB) and 180 mL of veratrole was heated to 60 C and pumped through the SILVERSON mixer.
- the organoclay composition comprising CLOISITE 15A (13.51 g), 4,4′-diaminodiphenyl sulfone (DDS) (33.90 g), and 1 mL acetic acid was added slowly to the recirculating solvent.
- the mixture was run through the SILVERSON high shear mixer at 6000 rpm for 45 minutes in recirculation mode.
- the solution temperature increased from 60 C to 86 C.
- the resulting solution was viscous indicating exfoliation of the organoclay.
- the mixture was transferred to a 1 L three-necked flask using 50 mL of oDCB to complete the transfer.
- the Flask was then equipped with an overhead stirrer and a Dean-Stark trap and placed in an oil bath that was heated to 140° C. 70.02 g of bisphenol A dianhydride (BPADA) was added in two portions over 15 minutes.
- the mixture was stirred and heated to reflux for 2 hours. The water removed by azeotropic distillation.
- BPADA bisphenol A dianhydride
- Phthalic anhydride (0.86 g) was added and allowed to react for 3 hours. A 10 g sample of the reaction mixture was the taken and the solvent was removed under nitrogen at 350° C. The residual polymer sample was pressed into a film and the infrared (IR) spectrum of the film was measured and the ratio of amine end-group to anhydride end-group was determined. From the IR spectrum it was found that the polymer sample contained 4.7 mole % excess anhydride. Using this information the reaction stoichiometry was adjusted by adding DDS (1.55 g) to correct for the excess anhydride content. The reaction mixture was then kept at 200° C. for 3 hours. An additional 0.6 g of DDS was added and allowed to react for 1 hour.
Abstract
wherein Ar1, Ar2, and Ar3 are independently C2-C50 aromatic radicals; Ar4 is a bond or a C2-C50 aromatic radical; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R1 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and R2 is a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C50 aromatic radical, or a polymer chain.
Description
wherein Ar1, Ar2, and Ar3 are independently C2-C50 aromatic radicals; Ar4 is a bond or a C2-C50 aromatic radical; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R1 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; R2 is a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C50 aromatic radical, or a polymer chain; and X− is a charge balancing counterion.
wherein X− is a charge balancing counterion, m is a number in a range from about 10 to about 1000, and Ar5 is a C2-C50 aromatic radical, or a polymer chain.
wherein Ar1, Ar2, Ar3 and Ar4 are independently C2-C50 aromatic radicals, and X− is a charge balancing counterion; with an anhydride compound having structure VII
“a” is a number from 1 to about 200; “c” is a number from 0 to 3; R1 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and R2 is a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C50 aromatic radical, or a polymer chain; and (b) isolating the product organophosphonium salt.
wherein “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R1 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and R2 is a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C50 aromatic radical, or a polymer chain; and (b) isolating the product organophosphonium salt.
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R3 and R4 are independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; Z is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group; Ar9 is a C10-C200 aromatic radical, or a polymer chain comprising at least one aromatic group; and X− is a charge balancing counterion.
wherein X− is independently at each occurrence a charge balancing counterion. In a particular embodiment X− is BF4 −.
wherein X− is independently at each occurrence a charge balancing counterion. In a particular embodiment X− is acetate.
wherein X− is a charge balancing counterion; “e” is a number in a range from about 10 to about 1000; and Ar10 is a C2-C50 aromatic radical, or a polymer chain. In a particular embodiment, X− is the tetrafluoroborate (BF4 −) anion, the variable “e” is about 100, and Ar10 is the C25-aromatic radical 2,4,6-triphenylpyridinium tetrafluoroborate. One of ordinary skill in the art will appreciate that an aromatic radical may include an associated counterion, here BF4 −, and still fall within the definition of the term aromatic radical as defined herein. Similarly, aliphatic radicals and cycloaliphatic radicals may include an associated counterion as well. Where a radical comprises multiple charges requiring the presence of a charge balancing counterion, a plurality of charge balancing counterions may be comprised within the radical. Those of ordinary skill in the art will appreciate as well that a fractional part of a charge balancing counterion may be comprised within a radical as well. For example in compositions in which a single positive charge is balanced by a divalent anion such as sulfate (SO4 =) a single sulfate anion may be associated with two individual molecules or radicals. Thus, in one embodiment, Ar10 is an aromatic radical comprising ½(SO4 =). In one embodiment, Ar10 is an aromatic radical having structure XIX
wherein X− is a charge balancing counterion. In a particular embodiment, X− is a fractional part of a divalent ion selected from the group consisting of sulfate, carbonate, and oxalate. In one embodiment, X− is ½(CO3 =), a fractional part of a carbonate anion.
wherein “d” is a number from 0 to 4; R4 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; Z is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group; Ar9 is a C10-C200 aromatic radical, or a polymer chain comprising at least one aromatic group; and X− is a charge balancing counterion;
with a pyrilium salt having structure XXI
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; R3 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and X− is a charge balancing counterion; and (b) isolating the product pyridinium salt having structure XV.
wherein X− is a charge balancing counterion; and
(b) isolating the product polymeric pyridinium salt having structure XXII.
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; R3 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and Ar11 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
TABLE III |
Illustrative Pyridinium Salts Comprising Cation XXV |
|
Entry | Ar6 | Ar7 | Ar8 | Ar11 | R3 | “b” | Counterion X− |
3a | Ph | Ph | Ph | Ph | — | 0 | BF4 − |
3b | Ph | H | Ph | 4-ClPh | MeO | 2 | Cl− |
3c | Ph | Ph | Ph | 4-CF3Ph | — | 0 | BF4 − |
3d | Ph | Ph | Ph | 2-pyridyl | — | 0 | BF4 − |
wherein Ar12, Ar13, Ar14 and Ar15 are independently C2-C50 aromatic radicals; and Ar16 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
TABLE IV |
Illustrative Phenone-Containing Salts Comprising Cation XXXIII |
|
Entry | Ar12 | Ar13 | Ar14 | Ar15 | Ar16 | Counterion X− |
4a | Ph | Ph | Ph | 1,4- | Ph | Cl− |
phenylene | ||||||
4b | Ph | Ph | Ph | 1,3- | Ph | Cl− |
phenylene | ||||||
4c | o- | o- | o- | 1,4- | 2- | I− |
tolyl | tolyl | tolyl | phenylene | napthyl | ||
4d | 3,4- | 3,4- | 3,4- | pyridine- | Ph | CF3SO3 − |
xylyl | xylyl | xylyl | 2,6-diyl | |||
wherein “g” and “h” are independently a number from 0 to 4; W is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group; R5 and R6 are independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; “i” is a number from about 10 to about 1000; and Ar17 is a C10-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein Ar1, Ar2, and Ar3 are independently C2-C50 aromatic radicals; Ar4 is a bond or a C2-C50 aromatic radical; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R1 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and R2 is a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C50 aromatic radical, or a polymer chain.
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R3 and R4 are independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; Z is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group; and Ar9 is a C10-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; R3 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; Ar11 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group; and X− is a charge balancing counterion;
is a quaternary organic salt comprising quaternary organic cation XXV
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; R3 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and Ar11 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein Ar12, Ar13, Ar14 and Ar15 are independently C2-C50 aromatic radicals; Ar16 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group; and X− is a charge balancing counterion; is a quaternary organic salt comprising a quaternary organic cation having structure
wherein Ar12, Ar13, Ar14 and Ar15 are independently C2-C50 aromatic radicals; and Ar16 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein Ar1, Ar2, and Ar3 are independently C2-C50 aromatic radicals; Ar4 is a bond or a C2-C50 aromatic radical; “a” is a number from 1 to about 200; “c” is a number from 0 to 3; R1 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and R2 is a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C50 aromatic radical, or a polymer chain.
wherein m is a number in a range from about 10 to about 1000; and Ar5 is a C2-C50 aromatic radical, or a polymer chain. In one embodiment, Ar5 is an aromatic radical having structure XIV.
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; R3 is independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and Ar11 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein Ar6, Ar7, and Ar8 are independently C2-C50 aromatic radicals; “b” is a number from 0 to 2; “d” is a number from 0 to 4; R3 and R4 are independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; Z is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group; and Ar9 is a C10-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein the variable “e” is a number from about 10 to about 1000; and Ar10 is a C2-C50 aromatic radical, or a polymer chain. In one embodiment, Ar10 is a C23 aromatic radical having structure XXX.
wherein “f” is a number from about 10 to about 1000. In a particular embodiment, “f” has a value of about 10. In another particular embodiment, “f” has a value of about 30.
wherein Ar12, Ar13, Ar14 and Ar15 are independently C2-C50 aromatic radicals; and Ar16 is a C2-C200 aromatic radical, or a polymer chain comprising at least one aromatic group.
wherein “g” and “h” are independently a number from 0 to 4; W is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group; R5 and R6 are independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; “i” is a number from about 10 to about 1000; and Ar17 is a C10-C200 aromatic radical, or a polymer chain comprising at least one aromatic group. In one embodiment, Ar17 is an aromatic radical having structure XXXVIII.
- 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;
- 2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;
- 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;
- 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;
- 4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;
- 4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;
- 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride;
- 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;
- 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;
- 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone dianhydride;
- 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;
- 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride;
- 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride;
- 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride;
- 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride;
- cyclobutane tetracarboxylic dianhydride;
- cyclopentane tetracarboxylic dianhydride;
- cyclohexane-1,2,5,6-tetracarboxylic dianhydride;
- 2,3,5-tricarboxycyclopentylacetic dianhydride;
- 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride;
- 1,3,3a,5-dioxo-3-furanyl)-naphtho[1,2,-c]-furan-1,3-dione;
- 3,5,6-tricarboxynorbornane-2-acetic dianhydride;
- 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride;
- 3,3′,4,4′-diphenyl tetracarboxylic dianhydride;
- 3,3′,4,4′-benzophenonetetracarboxylic dianhydride;
- naphthalic dianhydrides such as (2,3,6,7-naphthalic dianhydride etc.);
- 3,3′,4,4′-biphenylsulphonictetracarboxylic dianhydride;
- 3,3′,4,4′-biphenylethertetracarboxylic dianhydride;
- 3,3′,4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)diphenylsulphone dianhydride;
- 4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride;
- 3,3′,4,4′-perfluoropyridenediphthalic dianhydride;
- 3,3′, 4,4′-biphenyltetracarboxylic dianhydride;
- bis(phthalic)phenylsulphineoxide dianhydride;
- p-phenylene-bis(triphenylphthalic)dianhydride;
- m-phenylene-bis(triphenylphthalic)dianhydride;
- bis(triphenylphthalic)-4,4′-diphenylether dianhydride;
- bis(triphenylphthalic)-4,4′-diphenylmethane dianhydride;
- 2,2′-bis-(3,4-dicarboxyphenyl)hexafluoro-propane dianhydride;
- 4,4′-oxydiphthalic anhydride;
- pyromellitic dianhydride;
- 3,3′,4,4′-diphenylsulfone tetracarboxylic dianhydride;
- 4′,4′-bisphenol a dianhydride;
- hydroquinnone diphthalic anhydride;
- ethylene glycol bis trimellitic anhydride;
- 6,6′-bis(3,4-dicarboxyphenoxy)-2,2′,3,3′-tetrahydro-3,3,3′,3′-tetramethyl-1,1′-spirobi[1h-indene]dianhydride;
- 7,7′-bis(3,4-dicarboxyphenoxy)-3,3′,4,4′-tetrahydro-4,4,4′,4′-tetramethyl-2,2′-spirobi[2h-1-benzopyran]dianhydride;
- 1,1′-bis[1-(3,4-dicarboxyphenoxy)-2-methyl-4-phenyl]cyclohexane dianhydride;
- 3.3′,4,4′-diphenylsulfone tetracarboxylic dianhydride;
- 3.3′,4,4′-diphenylsulfide tetracarboxylic dianhydride;
- 3.3′,4,4′-diphenylsulfoxide tetracarboxylic dianhydride;
- 3,4′-oxydiphthalic anhydride;
- 3,3′-oxydiphthalic anhydride;
- 3,3′-benzophenone tetracarboxylic dianhydride;
- 4,4′-carbonyldiphthalic anhydride;
- 3.3′,4,4′-diphenylmethane tetracarboxylic dianhydride;
- 2,2-bis(4-(3,3-dicarboxyphenyl)propane dianhydride;
- 2,2-bis(4-(3,3-dicarboxyphenyl)hexafluoropropane dianhydride;
- (3,3′,4,4′-diphenyl)phenylphosphine tetracarboxylic dianhydride;
- (3,3′,4,4′-diphenyl)phenylphosphineoxide tetracarboxylic dianhydride;
- 2,2′-dichloro-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-dimethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-dicyano-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-dibromo-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-diiodo-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-ditrifluoromethyl-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-bis(1-methyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-bis(1-trifluoromethyl-2-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-bis(1-trifluoromethyl-3-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-bis(1-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 2,2′-bis(1-phenyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- 4,4′-bisphenol a dianhydride;
- 5,5′-[1,4-phenylenebis(oxy)]bis[1,3-isobenzofurandione];
- 3,3′,4,4′-diphenylsulfoxide tetracarboxylic dianhydride;
- 4,4′-carbonyldiphthalic anhydride;
- 3,3′,4,4′-diphenylmethane tetracarboxylic dianhydride;
- 2,2′-bis(1,3-trifluoromethyl-4-phenyl)-3,3′,4,4′-biphenyltetracarboxylic dianhydride;
- isomers thereof; and combinations thereof.
wherein Q is nitrogen or phosphorous; and R7, R8, R9, and R10 are independently a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C20 aromatic radical, or a polymer chain. In one embodiment, the quaternary organic cation having structure XXXIX is a quaternary phosphonium cation, for example the tetraphenyl phosphonium cation, TPP. In another embodiment, the quaternary organic cation having structure XXXIX is a quaternary phosphonium cation having structure X. In yet another embodiment, the quaternary organic cation having structure XXXIX is a quaternary phosphonium cation having structure XXXIII.
wherein “j” and “k” are independently a number from 0 to 3; R11 and R12 are independently at each occurrence a halogen atom, a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, or a C2-C20 aromatic radical; and W is a bond, a divalent C1-C20 aliphatic radical, a divalent C5-C20 cycloaliphatic radical, a divalent C2-C20 aromatic radical, an oxygen linking group, a sulfur linking group, a SO2 linking group, or a Se linking group.
wherein Q is nitrogen or phosphorous; and R7, R8, R9, and R10 are independently a C1-C20 aliphatic radical, a C5-C20 cycloaliphatic radical, a C2-C20 aromatic radical, or a polymer chain. Organoclay compositions comprising quaternary organic cations XXXIX are in certain instances commercially available. Alternatively, organoclay composition comprising quaternary organic cations XXXIX may be prepared using techniques disclosed herein.
Normalized CTE=CTE unfilled−(0.00444*CTE unfilled*wt % silicate),
and the percent exfoliation is given by
% Exfoliation=CTE filled(experimental measurement)/Normalized CTE.
TABLE 1 |
Organoclay Compositions Comprising Organophosphonium Cations |
d-Spacing | Wt loss at 400 deg C. under | ||
Example | Cation Modifier | (A) | N2 for 30 min (%) |
CE-1 | Tetraphenyl | 17.8 | 3.1 |
phosphonium | |||
CE-2 | 13 | 19 | 2.3 |
Ex-14 | 14 | 29 | 7.0 |
Ex-15 | 15 | 25.5 | 13.0 |
Ex-16 | 16 | 25.5 | 8.0 |
TABLE 2 |
Organoclay Compositions Comprising Monophosphonium Bisimide Cations |
d- | ||
Spacing | ||
Example | Cation Modifier | (A) |
Ex-17 |
|
17.5 |
Ex-18 |
|
19.57 |
Ex-19 |
|
15.05 |
Ex-20 |
|
18.3 |
TABLE 3 |
Organoclay Compositions Comprising Diphosphonium Bisimide Cations |
Example | Cation Modifier | d-Spacing (A) |
Ex-21 |
|
22.29 |
Ex-22 |
|
16.89 |
Ex-23 |
|
19.21 |
Ex-24 |
|
25.13 |
TABLE 4 |
Organoclay Compositions Comprising Amino-Phosphonium Monoimide |
Cations |
Example | Cation Modifier | d-Spacing (A) |
Ex-25 |
|
— |
Ex-26 |
|
17.27 |
TABLE 5 |
Polymer-Organoclay Composite Compositions |
Comprising Polyetherimide |
Example | Cation Modifier | d-spacing* | Mw | Mn | CTE |
30 | 21 | >30 | 47,785 | 23,175 | 28.7 |
31 | 23 | — | 50,458 | 25,079 | — |
32 | 24 | — | 43,295 | 19,641 | 40 |
33 | 14 | — | 51,729 | 25,094 | — |
34 | 22 | — | 49,518 | 23,753 | — |
35 | 17 | — | 51,628 | 24,362 | — |
36 | 18 | — | 51,246 | 25,286 | — |
37 | 19 | — | 50,449 | 26,621 | — |
d-spacing* in the polymer-organoclay composite composition |
TABLE 6 |
CTE results from in situ polymerization of DDS with ODPA and BPADA |
Compression molded samples. |
Cation | Clay | Mixing | |||||
Example | Dianhydride | Solvent | Modifier1 | Loading | Method† | CTE | % Ex‡ |
38 | BPADA | Orthodichorobenzene | NONE | 0% | NA | 58 | 0.0% |
39 | BPADA | Orthodichorobenzene | DP | 7% | Sonication | 37 | 34.2% |
40 | BPADA | oDCB | CUMYL | 7% | Sonication | 34 | 39.5% |
41 | BPADA | V* | TPP | 3.80% | Sonication | 48 | 15.8% |
42 | BPADA | NMP | TPP | 3.80% | Sonication | 47 | 17.5% |
43 | BPADA | O/V** | DP | 3.8 | Sonication | 44 | 22.8% |
44 | BPADA | O/V** | DP | 7.60% | Sonication | 36 | 35.7% |
45 | BPADA | oDCB | DP | 7% | Silverson | 50 | 11.0% |
46 | BPADA | oDCB | CUMYL | 7% | Silverson | 38 | 32.4% |
47 | BPADA | V* | CUMYL | 3.8 | Sonication | 45 | 21.0% |
48 | ODPA | oDCB | NONE | 0% | NA | 49 | 0.0% |
49 | ODPA | O/V** | DP | 3.80% | Sonication | 34 | 29.5% |
50 | ODPA | V* | TPP | 5% | Sonication | 39 | 18.6% |
51 | ODPA | O/V** | CUMYL | 3.8 | Sonication | 36 | 25.3% |
1“DP” = Cation 14, “CUMYL” = Cation 15, TPP = tetraphenylphosphonium | |||||||
†In Examples 45-46 the mixing step was carried out using a SILVERSON high shear mixer. | |||||||
‡“% Ex” percent exfoliation of the organoclay component in the polymer-organoclay composite composition. | |||||||
*“V” = veratrole. | |||||||
**“O/V**” = a mixture of oDCB and veratrole. |
TABLE 7 |
Yield Characterization Data for Pyridinium Salts |
TGA | ||||
Pyridinium Salt | Yield | 5 wt % Loss | ||
(abbreviation) | Starting Amine | % | m.p. (° C.) | Temp (° C.) |
27 | Aniline | 87 | 253 | 420 |
(TPPy-BF4) |
|
|||
28 | 4-Phenoxyaniline | 95 | 202 | 420 |
(Phenoxy-TPPy-BF4) |
|
|||
30 | Cumylphenoxyaniline | 94 | 284 | 420 |
(CumylPhenoxy-TPPy- BF4) |
|
|||
31 | BAPP | 95 | 354 | 400 |
(BAPP-TPPy-BF4) |
|
|||
TABLE 8 |
Elemental Analysis Of Pyridinium Modified Montmorillites |
Exp | Exp | Exp | Calc | Calc | |
Nanoclay | wt % of C | wt % of H | wt % Na | wt % C | wt % H |
Sodium | None | 2.46 | None |
montmorillite |
TPPy-MMT | 21.52 | 1.95 | 0.24 | 28.28 | 1.80 |
Phenoxy-TPPy- | 25.28 | 2.10 | 0.17 | 31.77 | 1.98 |
MMT | |||||
CumylPhenoxy- | 26.41 | 2.36 | 0.24 | 36.74 | 2.52 |
TPPY-MMT | |||||
BAPP-TPPy- | 24.65 | 2.09 | 0.17 | 32.52 | 2.10 |
MMT | |||||
TABLE 9 |
D-Spacing Of Organoclay Compositions And Percent Ion Exchange |
Percent Exchange (%) |
Based | Based | Based | d spacing | |
on C | on H | on Na | (Å) | |
Organoclay Composition | analysis | analysis | analysis | by XRD |
Sodium Montmorillite | — | — | — | 11 |
TPPy-MMT | 76 | 108 | 91 | 19 |
Phenoxy-TPPy-MMT | 80 | 106 | 94 | 19 |
CumylPhenoxy-TPPY-MMT | 72 | 94 | 91 | 23 |
BAPP-TPPy-MMT | 75 | 100 | 94 | 19 |
TABLE 10 |
GPC And CTE analysis of the extruded film |
Mp* | Mw | CTE 0-200° C. | ||
Sample | (Kg/mol) | (Kg/mol) | Mn (Kg/mol) | (ppm/° C.) |
Starting | 28.8 | 36.9 | 15.6 | N.A. |
material | ||||
Extruded Film | 50.5 | 52.2 | 20.7 | 50 |
*“peak molecular weight” |
The data gathered in Table 10 demonstrate that the molecular weight of polymer organoclay composition may be increased significantly by extrusion into a film.
TABLE 11 |
Polyimide Compositions Comprising CumylPhenoxy-TPPy-MMT |
Targeted | Anhydride/ | |||||||
Targeted | Mn | Amine | wt % | Mw | Mn | |||
Example | Polymer | Anhydride | Mw | (Kg/mol) | ratio | Silicate | (Kg/mol) | (Kg/mol) |
65 | ODPA-DDS | ODPA | 30 | 15.6 | 1.02 | 7 | 30.6 | 14.8 |
polyetherimide - | ||||||||
Hi | ||||||||
66 | ODPA-DDS | ODPA | 25 | 13.1 | 1.02 | 7 | 26.0 | 13.0 |
polyetherimide - | ||||||||
Lo | ||||||||
67 | BPADA-DDS | BPADA | 30 | 22.0 | 1.00 | 7 | 78.9 | 30.4 |
polyetherimide - | ||||||||
Hi | ||||||||
68 | BPADA-DDS | BPADA | 25 | 18.3 | 1.00 | 7 | 58.0 | 24.6 |
polyetherimide - | ||||||||
Lo | ||||||||
TABLE 12 |
Extruded Films Comprising Combinations Of Polyetherimides As The |
Polymeric Resin Component Of A Polymer-Organoclay Composite Composition |
Extruded Film |
Resin | CTEMD 1st |
Mw | Mn | Mw | Mn | heat, 0-200° C. | ||
Example | Polyimide Blend Compositions | (Kg/mol) | (Kg/mol) | (Kg/mol) | (Kg/mol) | (ppm/° C.) |
69 | 31 wt % ODPA- | 69 wt % BPADA- | 46.9 | 18.9 | 49.5 | 20.2 | nd* |
DDS | DDS polyetherimide - | ||||||
polyetherimide - Lo | Lo | ||||||
70 | 31 wt % ODPA- | 69 wt % BPADA- | 65.9 | 22.8 | 56.9 | 21.9 | nd |
DDS | DDS polyetherimide - | ||||||
polyetherimide - Hi | Lo | ||||||
71 | 31 wt % ODPA- | 69 wt % BPADA- | 46.3 | 19.1 | 51.8 | 21.2 | nd |
DDS | DDS polyetherimide - | ||||||
polyetherimide - Lo | Hi | ||||||
72 | 31 wt % ODPA- | 69 wt % BPADA- | 57.8 | 20.8 | 61.0 | 23.6 | 44 |
DDS | DDS polyetherimide - | ||||||
polyetherimide - Hi | Hi | ||||||
Control | 31 wt % PDFS48 | 69 wt % com. | 40.1 | 15.3 | 50.5 | 21.7 | 61 |
ODPA-DDS | BPADA-DDS | ||||||
polyetherimide | polyetherimide | ||||||
*nd = “not determined” |
TABLE 13 | |
Example |
Control | 76 | 77 | 78 | |
Polymeric resin | PEEK 450G | PEEK 450G | PEEK 450G | PEEK 450G |
Silicate Loading | 0% | 5% | 5% | 5% |
Organoclay composition | None | PhEK-MMT | Cumyl-MMT* | TPP-MMT** |
Weight % Silicate in Clay | 0% | 65% | 58% | 75% |
Weight Organoclay composition† | 0 grams | 16.92 grams | 18.97 grams | 14.67 grams |
Weight PEEK 450G | 220.00 grams | 203.08 grams | 201.3 grams | 205.33 grams |
Total Weight of Formulation | 220.00 grams | 220.00 grams | 220.00 grams | 220.00 grams |
*The preparation of the Organoclay composition Cumyl-MMT is given in Example 15. | ||||
**TPP-MMT is an organoclay composition derived from sodium montmorillonite clay and a tetraphenyl phosphonium halide salt |
TABLE 14 |
TEM Analysis Results |
Organoclay | Polymeric | ||
Example | composition | Resin | TEM Rating |
76 | PhEK-MMT | PEEK 450G | Good Dispersion |
77 | Cumyl-MMT | PEEK 450G | Poor Dispersion |
78 | TPP-MMT | PEEK 450G | Poor Dispersion |
TABLE 15 |
Polymer-Organoclay Composite Compositions |
Prepared By Melt Mixing |
Organoclay | Mixing | CTE of Film | ||
Example | Polymeric Resin | composition | Temperature | (30-230° C.) |
79 | PEEK 150P | BAPP-TPPy- | 380° C. | 67 ppm/° C. |
MMT | ||||
80 | PPSU* | BAPP-TPPy- | 340° C. | 61 ppm/° C. |
MMT | ||||
81 | PES** | BAPP-TPPy- | 330° C. | 54 ppm/° C. |
(ULTRASON | MMT | |||
E2010) | ||||
*PPSU = RADEL R, | ||||
**PES = POLYETHERSULFONE |
TABLE 16 |
CTE and Glass Transition Temperature (Tg) For Extruded Films |
Comprising A Polymer-Organoclay Composite Composition Containing As The |
Polymeric Component A 100% BPADA-DDS Polymer. |
% | % Exfoliation | No. | ||||||
Example | Silicate | Modifier | Process | CTE1 | CTE2 | MD/TD | Tg° C. | Extrusions |
Control | 0 | — | — | 58.2 | — | — | 2x | |
83 | 5 | TPP | Melt mix* | 48.4 | — | 15%/— | 2x | |
84 | 5 | 14 | Melt mix | 45.0 | — | 20.9%/— | 2x | |
85 | 10 | 14 | Melt mix | 39.9 | — | 28.2%/— | 2x | |
86 | 5 | 15 | Solvent | 48.7 | 50.9 | 14.5%/10.5% | 233 | |
mix** | ||||||||
87 | 10 | 15 | Solvent mix | 38.4 | 41.8 | 30.9%/24.9% | 226 | |
88 | 5 | 14 | In situ | 39.6 | 42.0 | 30.5%/26.3% | 240 | |
polym.† | ||||||||
89 | 10 | 14 | In situ | 33.7 | 34.2 | 39.3%/38.5% | 236 | |
polym. | ||||||||
90 | 5 | 15 | In situ | 39.9 | 44.6 | 29.9%/21.6% | 241 | |
polym. | ||||||||
91 | 10 | 15 | In situ | 31.6 | 33.5 | 43.1%/39.7% | 233 | |
polym. | ||||||||
92 | 5 | 15 | In situ | 39.2 | 44.9 | 31.2%/21.1% | 239 | |
polym. | ||||||||
93 | 5 | 15 | In situ | 43.6 | 45.2 | 23.3%/20.6% | 238 | |
polym. | ||||||||
*The melt mixing technique (See Examples 76-78) was used to prepare the polymer-organoclay composite composition. | ||||||||
**The solvent mixing technique (See Examples 52-53) was used to prepare the polymer-organoclay composite composition. | ||||||||
†The in situ polymerization technique (See Examples 27-29 and 38-51) was used to prepare the polymer-organoclay composite composition. |
Claims (23)
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